KR20100017382A - alphaMICROPOROUS FILMS FROM COMPATIBILIZED POLYMERIC BLENDS - Google Patents

Abstract

Disclosed herein are microporous films comprising polymer blends comprising at least two polymers and a compatibilizer. The films may also comprise at least one ethylene/α-olefin interpolymer and two different polyolefins which can be homopolymers. The ethylene/α-olefin interpolymers are block copolymers comprising at least a hard block and at least a soft block. In some embodiments, the ethylene/α-olefin interpolymer can function as a compatibilizer between the two polyolefins which may not be otherwise compatible. Methods of making the polymer blends and microporous films made from the polymer blends are also described.

Description

Α Microporous Films from Commercialized Polymer Blends {αMICROPOROUS FILMS FROM COMPATIBILIZED POLYMERIC BLENDS}

<Cross reference to related application>

This application takes precedence over US Provisional Patent Application No. 60 / 926,676, filed April 27, 2007. This application is also related to US patent application Ser. No. 11 / 516,390, filed September 6, 2006. Each of these applications is incorporated herein by reference in its entirety.

The present invention relates to a microporous film comprising a polymer blend prepared from two or more polymers and a compatibilizer, a method of making the film, and an article made from the film.

Microporous polymer films are used in many articles such as garments, shoes, filters, and battery separators.

In particular, such films can be useful for membrane filters. These filters are generally thin polymer films with many micropores. Membrane filters can be used to filter material suspended in liquids or gases or for quantitative separation. Examples of various types of membrane filters include gas separation membranes, dialysis / hemodialysis membranes, reverse osmosis membranes, ultrafiltration membranes and microporous membranes. Fields in which this type of membrane can be applied include analytical articles, beverages, chemicals, electronics, environmental articles and pharmaceuticals.

Microporous polymer films can also be used as battery separators due to ease of manufacture, chemical inertness and thermal properties. The main role of the separator is to allow ions to pass between the electrodes, but to prevent the electrodes from contacting. Therefore, the film must be strong so as not to pierce. In addition, for lithium-ion batteries, the film must be shut down at certain temperatures (disruption of ion conduction) to prevent overheating of the battery. Ideally, the resin used in the separator should have a high strength over a wide temperature range to enable thinner or more porous separators. In addition, for lithium ion batteries, lower shutdown temperatures are desirable, but the film must maintain mechanical integrity after shutdown. It is also desirable for the film to maintain dimensional stability at elevated temperatures.

Multiphase polymer blends are economically important in the polymer industry. Some examples of use of multiphase polymer blends include impact control of thermoplastics by dispersion of rubber modifiers into the thermoplastic matrix. In general, commercial polymer blends consist of two or more polymers and a small amount of compatibilizers or surfactants. Generally, compatibilizers or surfactants are block or graft copolymers that can promote the formation of small rubber domains in the polymer blend such that the impact strength is improved.

In many applications, blends of polypropylene (PP) and ethylene / α-olefin copolymers are used. The ethylene / α-olefin copolymers function as rubber modifiers in the blend and provide toughness and good impact strength. In general, the impact efficiency of ethylene / α-olefin copolymers is determined by the difference between a) the glass transition temperature (Tg) of the rubber modifier, b) the adhesion of the rubber modifier to the polypropylene interface, and c) the difference in viscosity of the rubber modifier and polypropylene. It can be a function. The Tg of the rubber modifier can be improved by various methods such as reducing the crystallinity of the α-olefin component. Similarly, the viscosity difference between the rubber modifier and the polypropylene can be optimized by various techniques such as controlling the molecular weight and molecular weight distribution of the rubber modifier. In the case of ethylene / high alpha-olefin (HAO) copolymers, the interfacial adhesion of the copolymer can be increased by increasing the amount of HAO. However, when the amount of HAO in the ethylene / HAO copolymer exceeds 55 mol%, the polypropylene becomes miscible with the ethylene / HAO copolymer and forms a single phase so that no small rubber domain is present. Thus, ethylene / HAO copolymers having a HAO greater than 55 mol% have limited utility as impact modifiers.

In the case of thermoplastic vulcanizates (TPV) in which rubber domains are crosslinked, it is desirable to improve properties such as compression set and tensile strength. These desirable properties can be improved by reducing the average rubber particle size. During the dynamic vulcanization step of TPV comprising polypropylene and polyolefin interpolymers, such as ethylene / alpha-olefin / diene terpolymers (eg ethylene / propylene / diene terpolymers (EPDM)), the terpolymer and poly There must be a compatibility balance of propylene. In general, EPDM has good compatibility with polypropylene, but the compatibility can be slightly improved by only increasing the propylene level in EPDM.

It would be useful to provide microporous polymer films with improved properties.

<Overview of invention>

The present invention,

(i) a first polymer;

(ii) a second polymer; And

(iii) an effective amount of a polymer compatibilizer

It provides a microporous film or membrane comprising at least one layer comprising a polymer blend comprising.

The invention also relates to a microporous film wherein the compatibilizer comprises an ethylene / α-olefin interpolymer and the first polyolefin, the second polyolefin and the ethylene / α-olefin interpolymer are different. When referring to two polyolefins the term “different” means that the composition (comonomer type, comonomer content, etc.), structure, properties or combinations thereof of the two polyolefins are different. For example, block ethylene / octene copolymers are different from random ethylene / octene copolymers even though they have the same amount of comonomers. Block ethylene / octene copolymers differ from ethylene / butane copolymers whether or not they are random or block copolymers or have the same comonomer content. In addition, two polyolefins are considered different if they have different molecular weights, even though they have the same structure and composition. In addition, the random homogeneous ethylene / octene copolymer is different from the random heterogeneous ethylene / octene copolymer, although all other parameters may be the same. In addition, the polymers are different when they have different densities by at least 0.002 g / cc. The polyolefin may have a molecular weight such that the molecular weight of the first polyolefin is about 0.5 to 10 times the molecular weight of the second polyolefin.

The ethylene / α-olefin interpolymers used in the microporous film have one or more of the following properties:

(a) Mw / Mn of about 1.7 to about 3.5, at least one melting point T _m (° C.), and density d (g / cm ³ ), where the values of T _m and d correspond to the following relationship:

T _m > -2002.9 + 4538.5 (d)-2422.2 (d) ² ); or

(b) Delta value ΔT (° C.), defined as the Mw / Mn of about 1.7 to about 3.5, and the heat of fusion ΔH (J / g), and the temperature difference between the highest DSC peak and the highest CRYSTAF peak (Where the values of ΔT and ΔH have the following relationship:

ΔT> -0.1299 (ΔH) + 62.81 (if ΔH is greater than 0 and less than or equal to 130 J / g),

ΔT ≧ 48 ° C. (if ΔH is greater than 130 J / g);

The crisp peak is determined using at least 5% of the cumulative polymer, and if less than 5% of the polymer has an identifiable crisp peak, the crisp temperature is 30 ° C.); or

(c) 300% strain and elastic recovery rate Re (%) at 1 cycle, and density d (g / cm ³ ) measured with a compression-molded film of ethylene / α-olefin interpolymers, wherein the values of Re and d Satisfies the following relationship when the ethylene / α-olefin interpolymer is substantially free of the crosslinked phase:

Re> 1481-1629 (d)); or

(d) molecular fractions eluted at 40 ° C. to 130 ° C. when fractionated using TREF (the fractions having at least 5% higher comonomer molar content than that of the comparative random ethylene interpolymer fractions eluting between the same temperatures) Wherein the comparative random ethylene interpolymer has the same comonomer (s) and has a melt index, density and comonomer molar content (based on total polymer) within 10% of that of the ethylene / α-olefin interpolymers ); or

(e) storage modulus G '(25 ° C.) at 25 ° C., and storage modulus G' (100 ° C.) at 100 ° C., where the ratio of G ′ (25 ° C.) to G ′ (100 ° C.) is about 1: In the range from 1 to about 10: 1); or

(f) at least one molecular fraction characterized by having a block index of at least 0.5 to about 1 and a molecular weight distribution Mw / Mn of greater than about 1.3 and eluting at 40 ° C. to 130 ° C. when fractionated using TREF; or

(g) an average block index greater than 0 and up to about 1.0 and a molecular weight distribution Mw / Mn greater than about 1.3; or

(h) Mw / Mn from about 1.7 to about 3.5, at least one melting point T _m (° C.), and density d (g / cm ³ ), where the values of T _m and d correspond to the following relationship:

T _m > -6553.3 + 13735 (d)-7051.7 (d) ² ).

In one embodiment, the ethylene / α-olefin interpolymer has a Mw / Mn of about 1.7 to about 3.5, at least one melting point T _m (° C.), and a density d (g / cm ³ ), wherein the values of T _m and d are Corresponds to the following relationship:

T _m ≥ 858.91-1825.3 (d) + 1112.8 (d) ² ).

In another embodiment, the ethylene / α-olefin interpolymer has a Mw / Mn of about 1.7 to about 3.5 and is defined as the heat of fusion ΔH (J / g), and the temperature difference between the highest DSC peak and the highest CRYSTAF peak. The delta value ΔT (° C), where the values of ΔT and ΔH have the following relationship:

ΔT> -0.1299 (ΔH) + 62.81 (if ΔH is greater than 0 and less than or equal to 130 J / g),

ΔT ≧ 48 ° C. (if ΔH is greater than 130 J / g);

The crisp peak is determined using at least 5% of the cumulative polymer, and if less than 5% of the polymer has an identified crisp peak, the crisp temperature is 30 ° C.).

In one embodiment, the ethylene / α-olefin interpolymer has a 300% strain and elastic recovery rate Re (%) at 1 cycle, measured with a compression-molded film of ethylene / α-olefin interpolymer, and a density d (g / cm ³ ) wherein the values of Re and d satisfy the following relationship when the ethylene / α-olefin interpolymers are substantially free of crosslinked phases:

Re> 1481-1629 (d), Re> 1491-1629 (d), Re> 1501-1629 (d) or Re> 1511-1629 (d).

In other embodiments, the ethylene / α-olefin interpolymers are molecular fractions eluted at 40 ° C. to 130 ° C. when fractionated using TREF, wherein the fractions are less than 5 of the comparative random ethylene interpolymer fractions eluted between the same temperatures. Characterized by having at least% higher comonomer molar content, the comparative random ethylene interpolymer having the same comonomer (s) and within 10% of that of the ethylene / α-olefin interpolymer Monomer molar content (based on total polymer).

In some embodiments, the ethylene / α-olefin interpolymer has a storage modulus G ′ (25 ° C.) at 25 ° C., and a storage modulus G ′ (100 ° C.) at 100 ° C., where G ′ (25 ° C.) versus G ′ (100 ° C.) ranges from about 1: 1 to about 10: 1.

In one embodiment, the ethylene / α-olefin interpolymer is a random block copolymer comprising one or more hard blocks and one or more soft blocks. In other embodiments, the ethylene / α-olefin interpolymer is a random block copolymer comprising a plurality of hard blocks and a plurality of soft blocks randomly distributed within the polymer chain.

In one embodiment, the α-olefin in the polymer blend provided herein is a C _4-40 α-olefin. In other embodiments, the α-olefin is styrene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, norbornene, 1-decene, 1,5-hexadiene or combinations thereof to be.

In some embodiments, the ethylene / α-olefin interpolymer has a melt index of about 0.1 to about 2000 g / 10 minutes (Mw of about 15,000 to about 200,000), measured according to ASTM D-1238 conditions 190 ° C./2.16 kg. 1 to about 1500 g / 10 min (Mw of about 16,000 to about 100,000), about 2 to about 1000 g / 10 min (Mw of about 18,000 to about 90,000), or about 5 to about 500 g / 10 min (about 22,000 To about 70,000 Mw).

In some embodiments, the amount of ethylene / α-olefin interpolymer in the polymer blends provided herein is about 0.5% to about 99%, about 1% to about 50%, about 2 to about 25% by weight of the total composition. %, About 3 to about 15 weight percent, or about 5 to about 10 weight.

In another embodiment, the ethylene / α-olefin interpolymer contains a soft segment having an α-olefin content of greater than 30 mol%, greater than 35 mol%, greater than 40 mol%, greater than 45 mol%, or greater than 55 mol%. do. In one embodiment, the elastomeric polymer contains a soft segment having an α-olefin content of greater than 55 mol%.

In some embodiments, the ethylene / α-olefin interpolymers in the polymer blend are elastomeric, having an ethylene content of 5 to 95 mol%, a diene content of 5 to 95 mol%, and an α-olefin content of 5 to 95 mol% Polymers. The α-olefins in the elastomeric polymer may be C _4-40 α-olefins.

In some embodiments, the amount of the first polyolefin in the polymer blend is about 0.5 to about 99 weight percent of the total weight of the polymer blend. In some embodiments, the amount of second polyolefin in the polymer blend is about 0.5 to about 99 weight percent of the total weight of the polymer blend.

In one embodiment, the first polyolefin is an olefin homopolymer such as polypropylene. Polypropylene as used herein includes, but is not limited to, low density polypropylene (LDPP), high density polypropylene (HDPP), high melt strength polypropylene (HMS-PP), high impact polypropylene (HIPP), isotactic ( isotactic polypropylene (iPP), syndiotactic polypropylene (sPP) and combinations thereof. In one embodiment, the polypropylene is isotactic polypropylene.

 In other embodiments, the first polyolefin and the second polyolefin have different densities.

In other embodiments, the second polyolefin is an olefin copolymer, olefin terpolymer or combinations thereof. The olefin copolymer can be derived from monoene and ethylene having 3 or more carbon atoms. Exemplary olefin copolymers are ethylene / alpha-olefin (EAO) copolymers and ethylene / propylene copolymers (EPM). The olefin terpolymers used in the polymer blends can be derived from ethylene, monoene having at least 3 carbon atoms, and dienes, including but not limited to ethylene / alpha-olefin / diene terpolymers (EAODM) and ethylene / propylene / dienes Terpolymer (EPDM). In one embodiment, the second polyolefin is a vulcanizable rubber.

In some embodiments, the polymer blend includes one or more additives, such as slips, antiblocking agents, plasticizers, antioxidants, UV stabilizers, colorants or pigments, fillers, lubricants, invincibles, flow aids, coupling agents, nucleating agents, interfacials. Further active agents, solvents, flame retardants, antistatic agents or combinations thereof.

Further, the polymer herein includes blending a first polyolefin, a second polyolefin, and an ethylene / α-olefin interpolymer, wherein the first polyolefin, second polyolefin, and ethylene / α-olefin interpolymers are different. Provided are methods of making the blends. The ethylene / α-olefin interpolymers used in the polymer blends are as described elsewhere herein and above.

Further aspects of the invention and the characteristics and properties of the various embodiments of the invention will become apparent from the following description.

1 shows the melting point / density relationship of the polymers of the present invention (indicated by rhombus) compared to conventional random copolymers (indicated by circles) and Ziegler-Natta copolymers (indicated by triangles).

FIG. 2 shows a plot of delta DSC-crystals as a function of DSC melt enthalpy for various polymers. Rhombus represents a random ethylene / octene copolymer; Squares represent Polymer Examples 1-4; Triangles represent Polymer Examples 5-9; Circles represent Polymer Examples 10-19. The symbol "X" represents Polymer Examples A ^* to F ^* .

FIG. 3 shows a non-oriented film comprising the inventive interpolymers (represented by squares and circles) and conventional copolymers (represented by triangles of various Dow AFFINITY® polymers). The effect of density on elastic recovery is shown. The square represents the ethylene / butene copolymer of the present invention, and the circle represents the ethylene / octene copolymer of the present invention.

FIG. 4 above the TREF elution temperature of the TREF fractionated ethylene / 1-octene copolymer fraction for the polymer of Example 5 (indicated by circle) and Comparative Examples E ^* and F ^* (indicated by symbol “X”). Plot of octene content of the fraction. Rhombus represents a conventional random ethylene / octene copolymer.

FIG. 5 is a plot of the octene content of the fraction versus the TREF elution temperature of the TREF fractionated ethylene / 1-octene copolymer fraction for the polymers of Example 5 (Curve 1) and Comparative Example F ^* (Curve 2). The square represents Example F ^* and the triangle represents Example 5.

FIG. 6 shows two ethylene / 1-octene block copolymers of the present invention made from comparative ethylene / 1-octene copolymer (curve 2) and propylene / ethylene-copolymer (curve 3) and different amounts of chain transfer agent ( It is a graph showing the log of storage modulus as a function of temperature for curve 1).

FIG. 7 shows a plot of TMA (1 mm) versus the flexural modulus of several inventive polymers (represented by rhombus) compared to some known polymers. The triangles represent various Versify (registered trademark) polymers (The Dow Chemical Company); Circles represent various random ethylene / styrene copolymers; Squares represent various affinity® polymers (The Dow Chemical Company).

8 is a plot of the natural log ethylene mole fraction for a random ethylene / α-olefin copolymer as the inverse of the DSC peak melting temperature or ATREF peak temperature. Filled squares represent data points obtained from random homogeneously branched ethylene / a-olefin copolymers in ATREF; Empty squares represent data points obtained from random homogenously branched ethylene / α-olefin copolymers in DSC. "P" is the mole fraction of ethylene and "T" is the Kelvin temperature.

FIG. 9 is a green plot based on the Flory equation for a random ethylene / α-olefin copolymer to illustrate the definition of “block index”. "A" represents a complete random copolymer; "B" represents pure "hard segment"; "C" refers to a complete block copolymer having a comonomer content equal to "A". A, B and C define the triangular region to which most TREF fractions belong.

10 is a transmission electron micrograph of a mixture of polypropylene and the ethylene / octene block copolymer of Example 20. FIG.

11 is a transmission electron micrograph of a mixture of polypropylene and a random ethylene / octene copolymer (Comparative Example A ¹ ).

12 is a transmission electron micrograph of a mixture of polypropylene, an ethylene-octene block copolymer (Example 20) and a random ethylene-octene copolymer (Comparative Example A ¹ ).

FIG. 13 is an image through a tapping mode AFM of a mixture of polypropylene and high density polyethylene.

14 is an image via tapping mode AFM of a mixture of polypropylene, high density polyethylene and a random ethylene / octene copolymer (Comparative Example B ¹ ).

FIG. 15 is an image via tapping mode AFM of a mixture of polypropylene and high density polyethylene and an ethylene / octene block copolymer (Polymer Example 21).

FIG. 16 is a plot of the stress versus strain of the three mixtures shown in FIGS. 11-13.

FIG. 17 is a low magnification (approximately 3,000 ×) scanning electron micrograph of the mixture shown in FIG. 13.

FIG. 18 is a high magnification (approximately 30,000 ×) scanning electron micrograph of the mixture shown in FIG. 13.

FIG. 19 is a low magnification (approximately 3,000 ×) scanning electron micrograph of the mixture shown in FIG. 14.

FIG. 20 is a high magnification (approximately 30,000 ×) scanning electron micrograph of the mixture shown in FIG. 14.

FIG. 21 is a low magnification (approximately 3,000 ×) scanning electron micrograph of the mixture shown in FIG. 15.

FIG. 22 is a high magnification (approximately 30,000 ×) scanning electron micrograph of the mixture shown in FIG. 15.

FIG. 23 is an image via tapping mode AFM of a mixture of 70 parts high density polyethylene and 30 parts random ethylene / octene copolymer (Comparative Example B ¹ ).

FIG. 24 is an image via tapping mode AFM of a mixture of 10 parts ethylene / octene block copolymer (polymer Example 22) and 65 parts high density polyethylene and 25 parts random ethylene / octene copolymer (Comparative Example B ¹ ).

FIG. 25 is a plot of the stress versus strain of the mixtures shown in FIGS. 23 and 24.

FIG. 26 is an image via low magnification (approximately 3,000 ×) tapping mode AFM of a mixture of 30 parts high density polyethylene and 70 parts random ethylene / octene copolymer (Comparative Example B ¹ ).

FIG. 27 is an image through high magnification (approximately 30,000 ×) tapping mode AFM of the mixture shown in FIG. 26.

FIG. 28 shows a low magnification (approximately 3000 ×) tapping mode AFM of a mixture of 10 parts ethylene / octene block copolymer (polymer example 22) and 27 parts high density polyethylene and 63 parts random ethylene / octene copolymer (Comparative Example B ¹ ) Through the image.

FIG. 29 is an image through high magnification (approximately 30,000 ×) tapping mode AFM of the mixture shown in FIG. 28.

30 is a plot of the stress versus strain of the mixtures shown in FIGS. 28 and 29.

General definition

"Polymer" means a polymeric compound prepared by the polymerization of monomers, whether of the same or a different kind. The general term "polymer" encompasses the terms "homopolymer", "copolymer", "terpolymer" as well as "interpolymer".

"Interpolymer" means a polymer prepared by the polymerization of two or more different monomers. The general term “interpolymer” is used in addition to the term “copolymer” (usually used to refer to a polymer made from two different monomers), as well as the term “terpolymer” (usually made from three different types of monomers). Used to refer to a polymer). It also encompasses polymers made by polymerizing four or more monomers.

The term "ethylene / α-olefin interpolymer" generally refers to a polymer comprising ethylene and an α-olefin having at least 3 carbon atoms. Preferably, ethylene comprises most of the mole fraction of the total polymer. In other words, ethylene comprises at least about 50 mol% of the total polymer. More preferably ethylene comprises at least about 60 mol%, at least about 70 mol%, or at least about 80 mol%, and the substantial remainder of the total polymer is occupied by at least one other comonomer, preferably an α-olefin having at least 3 carbon atoms. do. For many ethylene / octene copolymers, preferred compositions include an ethylene content of greater than about 80 mole percent of the total polymer and an octene content of about 10 to about 15, preferably about 15 to about 20 mole percent of the total polymer. do. In some embodiments, the ethylene / α-olefin interpolymers do not include those produced in low yields or in small amounts or by-products of chemical processes. The ethylene / α-olefin interpolymers may be blended with one or more polymers, but the resulting ethylene / α-olefin interpolymers are substantially pure and often included as a major component of the reaction product of the polymerization process.

Ethylene / α-olefin interpolymers comprise ethylene and one or more copolymerizable α-olefin comonomers in polymerized form and are characterized by multiple blocks or segments of two or more polymerized monomer units that differ in chemical or physical properties. do. In other words, the ethylene / α-olefin interpolymers are block interpolymers, preferably multi-block interpolymers or copolymers. They may be diblocks, treeblocks, or have two or more than three blocks. The terms "interpolymer" and "copolymer" are used interchangeably herein. In some embodiments, the multi-block copolymer can be represented by the formula:

(AB) _n

Wherein n is an integer greater than or equal to 1, preferably greater than 1, for example 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100 or As mentioned above, "A" represents a hard block or segment, and "B" represents a soft block or segment. Preferably, A and B are combined in a substantially linear fashion, as opposed to a substantially branched or substantially star-shaped fashion. In other embodiments, A blocks and B blocks are randomly distributed along the polymer chain. In other words, the block copolymer typically does not have a structure as follows.

AAA --AA -BBB --BB

In another embodiment, the block copolymers typically do not have a third type of block comprising different comonomer (s). In another embodiment, each of block A and block B has monomers or comonomers distributed substantially randomly within the block. In other words, neither block A nor block B contain two or more sub-segments (or sub-blocks) of distinct composition, such as tip segments, having a composition that is substantially different from the rest of the block.

The multi-block polymers typically include varying amounts of "hard" and "soft" segments. A “hard” segment refers to a block of polymerized units in which ethylene is present in an amount greater than about 95 weight percent, preferably greater than about 98 weight percent, based on the weight of the polymer. In other words, the comonomer content (content of monomers other than ethylene) in the hard segment is less than about 5% by weight, preferably less than about 2% by weight, based on the weight of the polymer. In some embodiments, the hard segments are all or substantially all ethylene. While “soft” segments have a comonomer content (content of monomers other than ethylene) of greater than about 5 weight percent, preferably greater than about 8 weight percent, greater than about 10 weight percent, or about 15 weight based on the weight of the polymer It refers to a block of polymerized units that are greater than%. In some embodiments, the comonomer content in the soft segment is greater than about 20 weight percent, greater than about 25 weight percent, greater than about 30 weight percent, greater than about 35 weight percent, greater than about 40 weight percent, greater than about 45 weight percent, about 50 Greater than or equal to about 60 weight percent.

Soft segments are often from about 1% to about 99%, preferably from about 5% to about 95%, from about 10% to about 90%, from about 15% to about 85% by weight of the total weight of the block interpolymer Weight percent, about 20 weight percent to about 80 weight percent, about 25 weight percent to about 75 weight percent, about 30 weight percent to about 70 weight percent, about 35 weight percent to about 65 weight percent, about 40 weight percent to about 60 Or from about 45% to about 55% by weight of the total weight of the block interpolymer can be present in the block interpolymer. In contrast, hard segments may exist in a similar range. Soft segment weight percentages and hard segment weight percentages can be calculated based on data obtained from DSC or NMR. The methods and calculations were filed on March 15, 2006 in the name of Colin LP Shan, Lonnie Hazlitt, et al. And assigned to Dow Global Technologies Inc. Is disclosed in US patent application Ser. No. 11 / 376,835, entitled "ethylene / α-olefin block interpolymers", which is incorporated herein by reference in its entirety.

The term "crystalline" when used refers to a polymer having a primary transition or crystalline melting point (T _m ) as determined by differential scanning calorimetry (DSC) or equivalent technique. The term may be used interchangeably with the term "semicrystalline". The term "amorphous" refers to a polymer having no crystalline melting point determined by differential scanning calorimetry (DSC) or equivalent technique.

The term "multi-block copolymer" or "segmented copolymer" is preferably a polymer comprising two or more chemically distinct regions or segments (referred to as "blocks"), ie pendant or By polymerized, rather than grafted, it is meant a polymer comprising chemically distinct units which are bonded end-to-end in polymerized ethylene-based functional groups. In a preferred embodiment, the block comprises the amount or type of comonomer incorporated therein, the density, the degree of crystallinity, the crystallite size contributing to the polymer of the composition, the type or extent of the tacticity (isotactic or syndiotactic), the regio The amount, homogeneity, or any other chemical or physical property of the branches, including regular or regio-irregular, long chain branching or hyper-branching. The multi-block copolymer is characterized by a unique distribution of all of the polydispersity index (PDI or Mw / Mn), block length distribution, and / or block number distribution due to the unique process of preparing the copolymer. More specifically, when prepared in a continuous process, the polymer preferably has a PDI of 1.7 to 2.9, preferably 1.8 to 2.5, more preferably 1.8 to 2.2 and most preferably 1.8 to 2.1. When prepared in a batch or semi-batch process, the polymer has a PDI of 1.0 to 2.9, preferably 1.3 to 2.5, more preferably 1.4 to 2.0, most preferably 1.4 to 1.8.

The term “porous” means having a microsized opening or cavity that is only visible under a microscope, typically having a lower diameter limit of about 0.03 μm to about 10 μm.

The term “microporous membrane” is defined as a thin walled structure having an open morphology of pore sizes ranging from about 0.03 μm to about 10 μm in diameter.

The term “compatibility agent” refers to a polymer that, when added to an immiscible polymer blend, can increase the miscibility of the two polymers, thereby increasing the stability of the blend. In some embodiments, when about 15% by weight of compatibilizer is added to the blend, the compatibilizer may reduce the average domain size by at least 20%, more preferably at least 30%, at least 40%, or at least 50%. In other embodiments, when about 15% by weight of compatibilizer is added to the blend, the compatibilizer is at least 10%, more preferably at least 20%, at least 30%, at least 40%, or 50 with miscibility of the two or more polymers. It can increase% or more. An “effective amount” of a compatibilizer means an amount such that the desired miscibility is achieved for a particular application.

The term “immiscible” refers to two polymers when a homogeneous mixture is not formed after mixing. In other words, phase separation occurs in the mixture. One way to quantify the immiscibility of two polymers is to use the Hildebrand solubility parameter, which is a measure of the total force that binds solid or liquid molecules together. Although not always available, all polymers are characterized by specific solubility parameter values. Polymers with similar solubility parameter values tend to be miscible. On the other hand, although there are many exceptions to the behavior, those with significantly different solubility parameters tend to be immiscible. A discussion of the solubility parameter concept is described in Encyclopedia of Polymer Science and Technology, Interscience, New York (1965), Vol. 3, pg. 833; (2) Encyclopedia of Chemical Technology, Interscience, New York (1971), Supp. Vol., Pg. 889; And (3) Polymer Handbook, 3rd Ed., J. Brandup and E. H. Immergut (Eds.), (1989), John Wiley & Sons "Solubility Parameter Values," pp. VII-519.

The term "surfactant" refers to an additive that reduces the interfacial energy between phase domains.

The term "olefin" refers to a hydrocarbon containing at least one carbon-carbon double bond.

By "propylene based polymer" is meant a polymeric compound comprising at least 50% by weight propylene. Examples of these are Versify (The Dow Chemical Company) and Vistamaxx (ExxonMobil Chemical Company).

The term “thermoplastic vulcanizate” (TPV) refers to an engineering thermoplastic elastomer in which the cured elastomeric phase is dispersed in a thermoplastic matrix. TPV generally comprises one or more thermoplastics and one or more cured (ie crosslinked) elastomeric materials. In some embodiments, the thermoplastic forms a continuous phase and the cured elastomer forms a discrete phase. That is, the domain of the cured elastomer is dispersed in the thermoplastic matrix. In other embodiments, the domain of the cured elastomer has a diameter of about 0.1 micrometers to about 100 micrometers, about 1 micrometer to about 50 micrometers; Between about 1 micrometer and about 25 micrometer; It is completely and uniformly dispersed in an average domain size ranging from about 1 micrometer to about 10 micrometers, or from about 1 micrometer to about 5 micrometers. In certain embodiments, the matrix phase of TPV is less than about 50 volume percent of TPV and the dispersed phase is at least about 50 volume of TPV. In other words, the crosslinked elastomeric phase is the major phase of TPV, while the thermoplastic polymer is the minor phase. TPVs with this phase composition can have good compression set. However, TPV may also be prepared wherein the main phase is a thermoplastic polymer and the secondary phase is a crosslinked elastomer. Generally, the cured elastomer has a moiety that is insoluble in cyclohexane at 23 ° C. The amount of insoluble portion is preferably greater than about 75% or about 85%. In some cases, the insoluble amount is greater than about 90 weight percent, greater than about 93 weight percent, greater than about 95 weight percent, or greater than about 97 weight percent of the total elastomer.

The term “polyethylene” includes ultra high molecular weight high density polyethylene (UHMWHDPE), high molecular weight polyethylene (HMWPE), high density polyethylene (HDPE), low density polyethylene (LDPE), homogeneous linear and linear low density polyethylene (LLDPE). "High molecular weight polyethylene" (HMWPE) means that the polyethylene has a Mw of at least 100,000 to about 1,000,000. "Ultra high molecular weight" means more than about 1 million and about 7 million Mw.

In the following description, all numbers disclosed herein are approximations regardless of whether the words "about" or "approximately" are used in this regard. Unless otherwise indicated, these values may vary by 1%, 2%, 5%, or often 10-20%, depending on the context described herein. In all cases where a numerical range having a lower limit R ^L and an upper limit R ^U is disclosed, any number falling within the range is specifically disclosed. In particular, the following numbers in the range are specifically disclosed: R = R ^L + k * (R ^U -R ^L ) wherein k is a variable in the range of 1% to 100% at 1% intervals, ie k Is 1%, 2%, 3%, 4%, 5%, ..., 50%, 51%, 52%, ..., 95%, 96%, 97%, 98%, 99%, or 100 %being). Moreover, any number range defined by two R numbers as defined above is also specifically disclosed.

Some embodiments of the present invention provide a microporous polymer film comprising a polymer blend comprising at least one ethylene / α-olefin interpolymer and at least two polyolefins. Ethylene / α-olefin interpolymers can improve the compatibility of two polyolefins which may be relatively incompatible. In other words, the interpolymer is a compatibilizer between two or more polyolefins.

Ethylene / α-olefin Interpolymers

The ethylene / α-olefin interpolymers (also referred to as “interpolymers of the invention” or “polymers of the invention”) used in embodiments of the invention are polymerized forms of ethylene and one or more copolymerizable α-olefin comonomers. Olefin interpolymers (block interpolymers), preferably multi-block copolymers, which are characterized by a plurality of blocks or segments of two or more polymerized monomer units which differ in chemical or physical properties. The ethylene / α-olefin interpolymers are characterized by one or more embodiments described below.

In one aspect, the ethylene / α-olefin interpolymers used in embodiments of the present invention have an M _w / M _n of about 1.7 to about 3.5 and at least one melting point T _m (° C.) and density d (g / cm ³ ). The numerical value of the variable corresponds to the following relation:

T _m > -2002.9 + 4538.5 (d)-2422.2 (d) ² , preferably

T _m ≥ -6288.1 + 13141 (d)-6720.3 (d) ² , more preferably

T _m ≥ 858.91 -1825.3 (d) + 1112.8 (d) ² .

In one aspect, the ethylene / α-olefin interpolymers used in embodiments of the present invention have an M _w / M _n of about 1.7 to about 3.5 and at least one melting point T _m (° C.) and density d (g / cm ³ ). The numerical value of the variable corresponds to the following relation:

T _m > -6553.3 + 13735 (d)-7051.7 (d) ² , preferably

T _m ≥ -6880.9 + 14422 (d)-7404.3 (d) ² , more preferably

T _m ≥ -7208.6-15109 (d)-7756.9 (d) ² .

The melting point / density relationship is illustrated in FIG. 1. Unlike conventional ethylene / a-olefin random copolymers, in which the melting point decreases with decreasing density, the interpolymers (denoted by rhombus) of the present invention, in particular when the density is from about 0.87 g / cc to about 0.95 g / cc, It shows a melting point that is substantially independent of density. For example, when the density is in the range of 0.875 g / cc to about 0.945 g / cc, the melting point of the polymer is in the range of about 110 ° C to about 130 ° C. In some embodiments, the melting point of the polymer is in the range of about 115 ° C. to about 125 ° C. when the density is in the range of 0.875 g / cc to about 0.945 g / cc.

In another embodiment, the ethylene / α-olefin interpolymer comprises ethylene and one or more α-olefins in polymerized form and has the highest crystallization analysis fractionation at the temperature for the highest differential scanning calorimetry (“DSC”) peak ( ΔT (° C.) and heat of fusion (J / g) ΔH, and ΔH, which are defined as minus the temperature for the “Crystal”) peak, and ΔH of 130 J / g, are characterized by satisfying the following relationship: :

ΔT> -0.1299 (ΔH) + 62.81, preferably

ΔT ≧ −0.1299 (ΔH) + 64.38, more preferably

ΔT ≧ −0.1299 (ΔH) +65.95.

Furthermore, ΔT is at least 48 ° C. when ΔH exceeds 130 J / g. The crisp peak is determined using at least 5% of the cumulative polymer (ie, the peak should represent at least 5% of the cumulative polymer), and if less than 5% of the polymer has an identified crisp peak, the crisp temperature Is 30 degreeC, and (DELTA) H is a numerical value of the heat of fusion represented by J / g. More preferably, the highest CRYSTAF peak contains at least 10% of the cumulative polymer. 2 shows plot data for the inventive polymers as well as the comparative examples. The integrated peak area and peak temperature are calculated by computerized drawing program supplied by the device manufacturer. The diagonal line shown for the random ethylene octene comparison polymer corresponds to the equation ΔT = -0.1299 (ΔH) + 62.81.

In another embodiment, the ethylene / α-olefin interpolymers have molecular fractions eluting at 40 ° C. to 130 ° C. when fractionated using Temperature Rising Elution Fractionation (“TREF”), the fractions being the same Characterized by having a comonomer molar content of at least 5% higher, more preferably at least 10% higher than that of the comparative random ethylene interpolymer fraction eluting in the temperature range, said comparative random ethylene interpolymer Contains the same comonomer (s) and has a melt index, density and comonomer molar content (based on total polymer) within 10% of that of the block interpolymer. Preferably, the Mw / Mn of the comparative interpolymer is also within 10% of the block interpolymer and / or the comparative interpolymer has a total comonomer content of within 10% by weight of the block interpolymer. .

In another embodiment, the ethylene / α-olefin interpolymers are characterized by 300% strain measured on a compression molded film of ethylene / α-olefin interpolymer and elastic recovery rate (Re) (%) in one cycle, Having a density (d) (g / cm ³ ), wherein the values of Re and d satisfy the following relationship when the ethylene / α-olefin interpolymer does not substantially comprise a crosslinked phase.

Re> 1481-1629 (d); Preferably

Re ≧ 1491-1629 (d); More preferably

Re ≧ 1501-1629 (d); Even more preferably

Re ≥ 1511-1629 (d).

3 shows the effect of density on elastic recovery for non-oriented films comprising certain interpolymers of the present invention and conventional random copolymers. At the same density, the inventive interpolymers have substantially higher elastic recovery.

In some embodiments, the ethylene / α-olefin interpolymer has a tensile strength greater than 10 MPa, preferably at least 11 MPa, more preferably at least 13 MPa, and / or has a cross of 11 cm / min. It has an elongation at break of at least 600%, more preferably at least 700%, very preferably at least 800% and most very preferably at least 900% at the head separation rate.

In another embodiment, the ethylene / α-olefin interpolymer has (1) a storage modulus ratio of G ′ (25 ° C.) / G ′ (100 ° C.) of 1 to 50, preferably 1 to 20, more preferably 1 To 10 and / or; (2) Compression set at 70 ° C. is less than 80%, preferably less than 70%, in particular less than 60%, less than 50%, or less than 40% to 0%.

In another embodiment, the ethylene / α-olefin interpolymer has a 70 ° C. compression set of less than 80%, less than 70%, less than 60%, or less than 50%. Preferably, the 70 ° C. compression set of the interpolymer is less than 40%, less than 30%, less than 20% and can be reduced to about 0%.

In some embodiments, the ethylene / α-olefin interpolymer has a heat of fusion less than 85 J / g, and / or 100 lb / ft ² (4800 Pa) or less, preferably 50 lb / ft ² (2400 Pa) Or less, in particular 5 lb / ft ² (240 Pa) or less as low as 0 lb / ft ² (0 Pa).

In other embodiments, the ethylene / α-olefin interpolymers comprise at least 50 mol% ethylene in polymerized form and have a 70 ° C. compression set of less than 80%, preferably less than 70%, or less than 60%, most Preferably it is less than 40-50% and decreases to near 0%.

In some embodiments, the multi-block copolymer has a PDI that fits the Schultz-Flory distribution but not the Poisson distribution. The copolymer has both a polydisperse block distribution and a polydisperse block size distribution, and is also characterized by having the most possible block length distribution. Preferred multi-block copolymers are those containing four or more blocks or segments, including end blocks. More preferably, the copolymer comprises five, ten or twenty or more blocks or segments, including end blocks.

Comonomer content can be measured using any suitable technique, with techniques based on nuclear magnetic resonance ("NMR") spectroscopy preferred. In addition, for polymers or polymer blends having a relatively wide TREF curve, first the TREF is used to fractionate the polymer into fractions each having an eluted temperature range of 10 ° C. or less. That is, each eluted fraction has a collection temperature window of 10 ° C. or less. Using this technique, the block interpolymer has one or more fractions having a higher comonomer molar content than that corresponding to the comparative interpolymer fraction.

In another embodiment, the polymer of the invention preferably comprises a plurality of blocks of two or more polymerized monomer units of different chemical or physical properties, i.e., comprising polymerized forms of ethylene and one or more copolymerizable comonomers (i.e., two Olefin interpolymers (block interpolymers), most preferably multi-block copolymers, characterized by at least two blocks) or segments, wherein the block interpolymers are from 40 ° C. to 130 ° C. (without collection and / or isolation of individual fractions). Has a peak eluting at (not just a molecular fraction), the peak has a comonomer content estimated by infrared spectroscopy upon expansion using a full width at half maximum (FWHM) area calculation and a full width at half maximum (FWHM) at the same elution temperature Higher, preferably at least 5% higher, more preferably higher than that of the comparative random ethylene interpolymer peak upon expansion using area calculation At least 10% higher comonomer average comonomer molar content, wherein the comparative random ethylene interpolymer has a melt index, density, and comonomer molar content (based on total polymer) within 10% for the block interpolymer It is characterized by having. Preferably, the Mw / Mn of the comparative interpolymer is also within 10% of the block interpolymer and / or the comparative interpolymer has a total comonomer content of within 10% by weight of the block interpolymer. Has The full width at half maximum (FWHM) calculation is based on the ratio of methyl to methylene response area [CH ₃ / CH ₂ ] from the ATREF infrared detector, where the largest (highest) peak is identified from the baseline, and then the FWHM area is determined. . For distributions measured using ATREF peaks, the FWHM area is defined as the area under the curve between T ₁ and T ₂ , where T ₁ and T ₂ are the ATREF curve, horizontal to the baseline after dividing the peak height by 2 Draw a line that intersects the left and right portions of, and determines the left and right sides of the ATREF peak. A calibration curve for comonomer content is made by plotting comonomer content from NMR against the FWHM area ratio of the TREF peak, using a random ethylene / α-olefin copolymer. In the case of the infrared method, a calibration curve is generated for the same comonomer type of interest. The comonomer content of the TREF peak of the polymer of the invention can be determined based on the calibration curve using the FWHM methyl: methylene area ratio [CH ₃ / CH ₂ ] of the TREF peak.

Comonomer content can be measured using any suitable technique, with techniques based on nuclear magnetic resonance (NMR) spectroscopy preferred. Using this technique, the block interpolymers have a higher comonomer molar content than the corresponding comparative interpolymers.

Preferably, for interpolymers of ethylene and 1-octene, the block interpolymers have a value of (-0.2013) T + 20.07 or more, more preferably of (-0.2013) T + 21.07 or more (wherein T Has a comonomer content of the TREF fraction eluting between 40 and 130 ° C., of which the peak elution temperature of the TREF fraction to be compared is measured in degrees Celsius.

FIG. 4 graphically illustrates embodiments of block interpolymers of ethylene and 1-octene, where plots of comonomer content against TREF elution temperatures of several comparative ethylene / 1-octene interpolymers (random copolymers) (-0.2013) fits well with the line (solid line) representing T + 20.07 The line for Equation (-0.2013) T + 21.07 is indicated by a dotted line. The comonomer content for the fractions of several block ethylene / 1-octene interpolymers (multi-block copolymers) of the present invention are also shown. All block interpolymer fractions have significantly higher 1-octene content than either line at equivalent elution temperatures. The above results are characteristic of the inventive interpolymers and are believed to be due to the presence of distinct blocks in the polymer chain having both crystalline and amorphous properties.

FIG. 5 graphically shows the TREF curve and comonomer content of polymer fractions for Example 5 and Comparative Example F ^* described below. For both polymers the peak eluting at 40-130 ° C., preferably 60-95 ° C., is separated into three parts, each part eluting over a temperature range of less than 10 ° C. The actual data of Example 5 is shown by a triangle. Those skilled in the art will appreciate appropriate calibration curves for interpolymers containing different comonomers, and TREF values obtained from random copolymers prepared using comparative interpolymers of the same monomer, preferably metallocene or other homogeneous catalyst compositions. It will be appreciated that the line used as a comparison that fits well can be constructed. The interpolymers of the present invention are characterized by a comonomer molar content that is greater than the value determined from the calibration curve at the same TREF elution temperature, preferably at least 5% larger, more preferably at least 10% larger.

In addition to the above aspects and properties described herein, the polymers of the present invention may be characterized by one or more additional features. In one aspect, the polymer of the present invention preferably comprises ethylene and one or more copolymerizable comonomers in polymerized form and comprises a plurality of blocks or segments of two or more polymerized monomer units having different chemical or physical properties. Characterized olefin interpolymers (block interpolymers), most preferably multi-block copolymers, wherein the block interpolymers have a molecular fraction eluting at 40 ° C. to 130 ° C. and when fractionated using TREF increments Is a higher molar comonomer content, preferably at least 5% higher, more preferably at least 10%, 15%, 20% or 25% higher than that of the comparative random ethylene interpolymer fraction eluting between the same temperatures. Wherein the comparative random ethylene interpolymer comprises the same comonomer (s), preferably the same comonomer ( ), And a melt index of less than 10% of that of the block copolymer, is characterized as having a density, and molar comonomer content (based on the total polymer). Preferably, the Mw / Mn of the comparative interpolymer is also within 10% of that of the block interpolymer and / or the comparative interpolymer has a total comonomer content within 10% by weight of that of the block interpolymer. .

Preferably, the interpolymers are interpolymers of ethylene and at least one α-olefin, in particular these interpolymers have an overall polymer density of about 0.855 to about 0.935 g / cm ³ , more particularly about 1 mol% For polymers with excess comonomers, the block interpolymers have a value of (-0.1356) T + 13.89 or more, more preferably of (-0.1356) T + 14.93, most preferably (-0.2013) T Has a comonomer content of the TREF fraction eluting between 40 and 130 ° C. above a value of +21.07, where T is the value of the peak ATREF elution temperature of the compared TREF fraction in ° C.

Preferably, the interpolymers of ethylene and at least one α-olefin, especially those copolymers having an overall polymer density of from about 0.855 to about 0.935 g / cm ³ , more particularly more than about 1 mol% For polymers with monomers, the block interpolymer has a value of at least (-0.2013) T + 20.07, more preferably a value of (-0.2013) T + 21.07, where T is the peak elution temperature of the TREF fraction being compared. Is the value measured in ° C.) and the comonomer content of the TREF fraction eluting between 40 and 130 ° C.

In another embodiment, the polymers of the present invention preferably comprise ethylene and at least one copolymerizable comonomer in polymerized form and in multiple blocks or segments of two or more polymerized monomer units having different chemical or physical properties. Characterized olefin interpolymers (block interpolymers), most preferably multi-block copolymers, wherein the block interpolymers have a molecular fraction eluting at 40 ° C. to 130 ° C. when fractionated using TREF increments, and at least about 6 Each fraction having a comonomer content of mol% has a melting point of greater than about 100 ° C. For these fractions having a comonomer content of about 3 mol% to about 6 mol%, each fraction has a DSC melting point of about 110 ° C. or greater. More preferably, the polymer fraction with at least 1 mol% comonomer has a DSC melting point corresponding to the following formula:

T _m ≧ (−5.5926) (mol% of comonomer in fraction) +135.90.

In another embodiment, the polymers of the present invention preferably comprise ethylene and at least one copolymerizable comonomer in polymerized form and in multiple blocks or segments of two or more polymerized monomer units having different chemical or physical properties. Characterized olefin interpolymers (block interpolymers), most preferably multi-block copolymers, wherein the block interpolymers have a molecular fraction eluting from 40 ° C. to 130 ° C. when fractionated using TREF increments, about 76 ° C. Each fraction having an ATREF elution temperature above is characterized by having a melting enthalpy (heat of fusion) measured by DSC, corresponding to the following equation:

Heat of fusion (J / gm) ≤ (3.1718) (ATREF elution temperature (° C)) -136.58

The block interpolymers of the present invention have molecular fractions that elute at 40 ° C. to 130 ° C. when fractionated using TREF increments, and each fraction having an ATREF elution temperature between 40 ° C. and less than about 76 ° C. corresponds to , Characterized by having a melt enthalpy (heat of fusion) measured by DSC:

Heat of fusion (J / gm) ≤ (1.1312) (ATREF elution temperature (° C)) + 22.97.

ATREF peak comonomer composition measurement by infrared detector

The comonomer composition of the TREF peak can be measured using an IR4 infrared detector available from Polymer Char, Valencia, Spain ( http://www.polymerchar.com/ ).

The "composition mode" of the detector is equipped with a measuring sensor (CH ₂ ) and a composition sensor (CH ₃ ), which are fixed narrow band infrared filters in the region of 2800 to 3000 cm ^-1 . The measurement sensor detects methylene (CH ₂ ) carbon on the polymer (directly related to the polymer concentration in solution) while the composition sensor detects the methyl (CH ₃ ) group of the polymer. The mathematical ratio of the composition signal (CH ₃ ) divided by the measurement signal (CH ₂ ) is sensitive to the comonomer content of the measured polymer in solution and the response is corrected with a known ethylene α-olefin copolymer standard.

When used with an ATREF instrument, the detector provides both the concentration (CH ₂ ) and composition (CH ₃ ) signal responses of the polymer eluted during the TREF process. Polymer specific correction can be made by measuring the area ratio of CH ₃ to CH ₂ with known comonomer content (preferably by NMR) for the polymer. The comonomer content of the ATREF peak of the polymer can be estimated by applying a baseline correction of the area ratio for the individual CH ₃ and CH ₂ responses (ie, the CH ₃ / CH ₂ area ratio to comonomer content).

Peak areas can be calculated using full width at half maximum (FWHM) calculations after applying an appropriate baseline to integrate the individual signal responses from the TREF chromatogram. The full width at half maximum is based on the ratio [CH ₃ / CH ₂ ] of methyl to methylene response area from the ATREF infrared detector, where the largest (highest) peak is identified from the baseline and then the FWHM area is determined. For distributions measured using ATREF peaks, the FWHM area is defined as the area under the curve between T1 and T2, where T1 and T2 are the peak height divided by 2, and then the left side of the ATREF curve, horizontal to the baseline, and A line intersecting with the right part is drawn to determine the left and right sides of the ATREF peak.

The application of infrared spectroscopy to determine the comonomer content in polymers in the ATREF-IR method is, in principle, described in Markovich, Ronald P .; Hazlitt, Lonnie G .; Smith, Linley; "Development of gel-permeation chromatography-Fourier transform infrareds spectroscopy for characterization of ethylene-based polyolefin copolymers". Polymeric Materials Science and Engineering (1991), 65, 98-100 .; and Deslauriers, P. J .; Rohlfing, D. C .; Shieh, E. T .; Of GPC / FTIR systems as described in "Quantifying short chain branching microstructures in ethylene-1-olefin copolymers using size exclusion chromatography and Fourier transform infrared spectroscopy (SEC-FTIR)", Polymer (2002), 43, 59-170. And both documents are incorporated herein by reference in their entirety.

In other embodiments, the ethylene / α-olefin interpolymers of the invention are characterized by an average block index ABI of greater than 0 and up to about 1.0 and a molecular weight distribution M _w / M _n of greater than about 1.3. The average block index ABI is the weight average of the block index (“BI”) for each polymer fraction obtained in the preparative TREF at intervals of 5 ° C. from 20 ° C. to 110 ° C .:

ABI = ∑ ( w _i BI _i )

Wherein BI _i is the block index for the i th fraction of the ethylene / α-olefin interpolymers of the invention obtained in the preparative TREF, and w _i is the weight percentage of the i th fraction.

For each polymer fraction, BI is defined by one of the following two equations (both give the same BI value):

, P_A는 1이다.Wherein T _X is the preparative ATREF elution temperature (preferably expressed in Kelvin) for the i th fraction, and P _X is the ethylene mole fraction for the i th fraction that can be measured by NMR or IR as above. P _AB is also the ethylene mole fraction of the total ethylene / α-olefin interpolymer (before fractionation) which can be measured by NMR or IR. T _A and P _A are the ATREF elution temperature and ethylene mole fraction for pure “hard segments” (called the crystalline segments of the interpolymer). In the first rule of thumb, if the actual values for the "hard segments" are not available, the T _A and P _A values are set to the values for the high density polyethylene homopolymer. For calculations performed herein, T _A is 372

, P _A is 1.

T _AB is the ATREF temperature for a random copolymer of the same composition with an ethylene mole fraction of P _AB . T _AB can be calculated from the following equation.

Ln P _AB = α / T _AB + β

Wherein α and β are two constants that can be determined by calibration with a number of known random ethylene copolymers. It should be noted that α and β may vary from instrument to instrument. In addition, there is a need to generate calibration curves by the polymer composition of interest and also in similar molecular weight ranges for the fractions. There is a slight molecular weight effect. If the calibration curve is obtained from similar molecular weight ranges, this effect is essentially negligible. In some embodiments, the random ethylene copolymer satisfies the following relationship.

Ln P = -237.83 / T _ATREF + 0.639

T _XO is the ATREF temperature for a random copolymer of the same composition with an ethylene mole fraction of P _X. T _XO can be calculated from LnP _X = α / T _XO + β. Conversely, P _XO is the ethylene mole fraction for random copolymers of the same composition whose ATREF temperature is T _X (which can be calculated from Ln P _XO = α / T _X + β).

Once the block index (BI) for each preparative TREF fraction is obtained, the weight average block index (ABI) for the entire polymer can be calculated. In some embodiments, ABI is greater than zero but less than about 0.3, or from about 0.1 to about 0.3. In other embodiments, ABI is greater than about 0.3 and up to about 1.0. Preferably, the ABI should range from about 0.4 to about 0.7, about 0.5 to about 0.7, or about 0.6 to about 0.9. In some embodiments, ABI ranges from about 0.3 to about 0.9, about 0.3 to about 0.8, about 0.3 to about 0.7, about 0.3 to about 0.6, about 0.3 to about 0.5, or about 0.3 to about 0.4. In other embodiments, ABI ranges from about 0.4 to about 1.0, about 0.5 to about 1.0, about 0.6 to about 1.0, about 0.7 to about 1.0, about 0.8 to about 1.0, or about 0.9 to about 1.0.

Another feature of the ethylene / α-olefin interpolymers of the present invention is that the ethylene / α-olefin interpolymers of the present invention have a block index of greater than about 0.1 to about 1.0 or less, which can be obtained by preparative TREF, M _w / M _n ) at least one polymer fraction greater than about 1.3. In some embodiments, the polymer fraction has a block index greater than about 0.6 and up to about 1.0, greater than about 0.7 and up to about 1.0, greater than about 0.8 and up to about 1.0, or greater than about 0.9 and up to about 1.0. In other embodiments, the polymer fraction has a block index greater than about 0.1 and up to about 1.0, greater than about 0.2 and up to 1.0, greater than about 0.3 and up to 1.0, greater than about 0.4 and up to 1.0, or greater than about 0.4 and up to 1.0. In another embodiment, the polymer fraction has a block index greater than about 0.1 and up to about 0.5, greater than about 0.2 and up to about 0.5, greater than about 0.3 and up to about 0.5, or greater than about 0.4 and up to about 0.5. In another embodiment, the polymer fraction has a block index greater than about 0.2 and up to about 0.9, greater than about 0.3 and up to about 0.8, greater than about 0.4 and up to about 0.7, or greater than about 0.5 and up to about 0.6.

With respect to the copolymer of ethylene and α-olefin, the polymer of the present invention is preferably (1) 1.3 or more, more preferably 1.5 or more, 1.7 or more, 2.0 or more, most preferably 2.6 or more, maximum 5.0 or less, and more. PDI preferably at most 3.5, in particular at most 2.7; (2) heat of fusion of up to 80 J / g; (3) an ethylene content of at least 50% by weight; (4) has a glass transition temperature (T _g ) of less than -25 ° C, more preferably less than -30 ° C, and / or (5) one, also a single, T _m .

In addition, the polymer of the present invention may have a storage modulus (G ′) alone or in combination with any other property such that log (G ′) is 400 kPa or more, preferably 1.0 MPa or more at a temperature of 100 ° C. Can be. In addition, the polymers of the present invention have a relatively uniform storage modulus as a function of temperature in the range from 0 to 100 ° C. (shown in FIG. 6), which is a property of the block copolymers, which means that olefin copolymers, in particular ethylene and at least one C _It is not known so far for copolymers of _3-8 aliphatic α-olefins (in this context, the term “relatively uniform” means that the log G ′ (in Pascal units) is between 50 and 100 ° C., preferably between 0 and 100 ° C. Decreases by less than one digit).

The interpolymers of the present invention may be further characterized by a thermomechanical analysis penetration depth of 1 mm and a flexural modulus of 3 kpsi (20 MPa) to 13 kpsi (90 MPa) at temperatures above 90 ° C. Otherwise, the inventive interpolymers can have a thermomechanical analysis penetration depth of 1 mm and a flexural modulus of at least 3 kpsi (20 MPa) at temperatures of 104 ° C. or higher. They may be characterized as having wear resistance (or volume loss) of less than 90 mm ³ . 7 shows the TMA (1 mm) for the flexural modulus of the polymers of the present invention compared to other known polymers. The polymers of the present invention have a significantly better flex-heat resistance balance than other polymers.

In addition, the ethylene / α-olefin interpolymers may be used in an amount of 0.01 to 2000 g / 10 minutes, preferably 0.01 to 1000 g / 10 minutes, more preferably 0.01 to 500 g / 10 minutes, especially 0.01 to 100 g / 10 minutes. May have a melt index (I ₂ ). In certain embodiments, the ethylene / α-olefin interpolymer has 0.01 to 10 g / 10 minutes, 0.5 to 50 g / 10 minutes, 1 to 30 g / 10 minutes, 1 to 6 g / 10 minutes, or 0.3 to 10 g Melt index (I ₂ ) of 10 minutes. In certain embodiments, the melt index of the ethylene / α-olefin polymer is 1 g / 10 minutes, 3 g / 10 minutes or 5 g / 10 minutes.

The polymer may be from 1,000 g / mol to 5,000,000 g / mol, preferably from 1000 g / mol to 1,000,000 g / mol, more preferably from 10,000 g / mol to 500,000 g / mol, in particular from 10,000 g / mol to 300,000 g / mol It may have a molecular weight (M _w ). In addition, the polymer may have a Mw of about 100,000 g / mol or less, and in other embodiments may have a Mw of about 3,000,000 g / mol or less. The density of the polymer of the invention may be 0.80 to 0.99 g / cm ³ , preferably 0.85 g / cm ³ to 0.97 g / cm ³ for ethylene containing polymers. In certain embodiments, the density of the ethylene / α-olefin polymer is in the range of 0.860 to 0.925 g / cm ³ or 0.867 to 0.910 g / cm ³ .

Processes for preparing polymers are disclosed in the following patent applications: US Provisional Application No. 60 / 553,906, filed March 17, 2004; 60 / 662,937, filed March 17, 2005; 60 / 662,939, filed March 17, 2005; 60/5662938, filed March 17, 2005; PCT Application No. PCT / US2005 / 008916, filed March 17, 2005; PCT / US2005 / 008915, filed March 17, 2005; And PCT / US2005 / 008917, filed March 17, 2005, all of which are incorporated herein by reference in their entirety. For example, one such method involves the process of adding ethylene and optionally one or more addition polymerizable monomers other than ethylene under addition polymerization conditions,

(A) a first olefin polymerization catalyst having a high comonomer incorporation index,

(B) a second olefin polymerization catalyst having a comonomer incorporation index of less than 90%, preferably less than 50%, most preferably less than 5% of the comonomer incorporation index of catalyst (A), and

(C) chain transfer agent

Mixture or reaction product produced by combining

It comprises contacting with a catalyst composition comprising a.

Representative catalysts and chain transfer agents are as follows.

Catalyst (A1) : [N- (2,6-di (1-methyl), prepared according to the teachings of WO 03/40195, 2003US0204017, USSN 10 / 429,024 (filed May 2, 2003) and WO 04/24740. Ethyl) phenyl) amido) (2-isopropylphenyl) (α-naphthalene-2-diyl (6-pyridin-2-diyl) methane)] hafnium dimethyl.

Catalyst (A2) : [N- (2,6-di (1-methyl), prepared according to the teachings of WO 03/40195, 2003US0204017, USSN 10 / 429,024 (filed May 2, 2003) and WO 04/24740. Ethyl) phenyl) amido) (2-methylphenyl) (1,2-phenylene- (6-pyridin-2-diyl) methane)] hafnium dimethyl.

Catalyst (A3) : Bis [N, N '"-(2,4,6-tri (methylphenyl) amido) ethylenediamine] hafnium dibenzyl.

Catalyst (A4) : Bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl substantially prepared according to the teachings of US-A-2004 / 0010103 ) -2-phenoxymethyl) cyclohexane-1,2-diyl zirconium (IV) dibenzyl.

Catalyst (B1) : 1,2-bis- (3,5-di-t-butylphenylene) (1- (N- (1-methylethyl) imino) methyl) (2-oxoyl) zirconium dibenzyl .

Catalyst (B2): 1,2-bis- (3,5-di-t-butylphenylene) (1- (N- (2-methylcyclohexyl) -imino) methyl) (2-oxoyl) zirconium Dibenzyl.

Catalyst (C1) : (t-butylamido) dimethyl (3-N-pyrrolyl-1,2,3,3a, 7a-η-indene-1- substantially prepared according to the teachings of US Pat. No. 6,268,444 (1) silane titanium dimethyl.

Catalyst (C2) : (t-butylamido) di (4-methylphenyl) (2-methyl-1,2,3,3a, 7a-η substantially prepared according to the teachings of US-A-2003 / 004286 Inden-1-yl) silanetitanium dimethyl.

Catalyst (C3) : (t-butylamido) di (4-methylphenyl) (2-methyl-1,2,3,3a, 8a-η substantially prepared according to the teachings of US-A-2003 / 004286 -s-indasen-1-yl) silanetitanium dimethyl.

Catalyst (D1) : Bis (dimethyldisiloxane) (inden-1-yl) zirconium dichloride available from Sigma-Aldrich.

Transfer Agents: The transfer agents used are diethylzinc, di (i-butyl) zinc, di (n-hexyl) zinc, triethylaluminum, trioctylaluminum, triethylgallium, i-butylaluminum bis (dimethyl (t-butyl) ) Siloxane), i-butylaluminum bis (di (trimethylsilyl) amide), n-octylaluminum di (pyridine-2-methoxide), bis (n-octadecyl) i-butylaluminum, i-butylaluminum bis ( Di (n-pentyl) amide), n-octyl aluminum bis (2,6-di-t-butylphenoxide, n-octyl aluminum di (ethyl (l-naphthyl) amide), ethyl aluminum bis (t-butyl Dimethylsiloxide), ethylaluminum di (bis (trimethylsilyl) amide), ethylaluminum bis (2,3,6,7-dibenzo-l-azacycloheptanamide), n-octylaluminum bis (2,3, 6,7-dibenzo-l-azacycloheptanamide), n-octylaluminum bis (dimethyl (t-butyl) siloxide, ethylzinc (2,6-diphenylphenoxide) and ethylzinc (t-butoxide ) Is included.

Preferably, the process comprises a block copolymer, in particular a multi-block copolymer, preferably two or more monomers, more particularly ethylene and C _3-20 olefins or cycloolefins, using a plurality of catalysts which are not interconvertible, Most particularly it takes the form of a continuous solution process for the formation of linear multi-block copolymers of ethylene and C _4-20 α-olefins. That is, the catalyst is chemically different. Under continuous solution polymerization conditions, the process is ideally suited for the polymerization of monomer mixtures with high monomer conversion. Under these polymerization conditions, the transfer from the chain transfer agent to the catalyst is favored over chain growth, and multi-block copolymers, especially linear multi-block copolymers, are formed with high efficiency.

The interpolymers of the present invention can be distinguished from conventional random copolymers, physical blends of polymers, and block copolymers prepared by sequential monomer addition, flowable catalysts, anionic or cationic living polymerization techniques. In particular, compared to random copolymers having the same monomers and monomer content at equivalent crystallinity or elastic modulus, the inventive interpolymers have better (high) heat resistance, higher TMA penetration temperature, higher hot tension as measured by melting point. Higher hot torsional storage modulus determined by strength, and / or thermomechanical analysis. Compared to random copolymers having the same monomers and monomer content, the interpolymers of the invention have lower compression set, lower stress relaxation, higher creep resistance, higher tear strength, higher blocking resistance, especially at elevated temperatures, Faster set-up due to higher crystallization (solidification) temperature, higher recovery rate (especially at elevated temperatures), better wear resistance, higher shrinkage, and better oil and filler tolerance.

The interpolymers of the present invention also exhibit unique crystallization and branching distribution relationships. In other words, the interpolymers of the present invention contain, in particular, the same monomers and monomer levels or physical blends of polymers, for example, in comparison with random copolymers containing equal overall density of blends of high density polymers and low density copolymers. Has a relatively large difference between the highest peak temperatures measured as a function of heat of fusion. This unique feature of the inventive interpolymers is believed to be due to the unique distribution of comonomers in the blocks within the polymer backbone. In particular, the inventive interpolymers may include alternating blocks (including homopolymer blocks) having different comonomer contents. The interpolymers of the present invention may also include a distribution in the number and / or block size of polymer blocks having different densities or comonomer contents, which is a Schulz-Flori type distribution. In addition, the inventive interpolymers also have unique peak melting points and crystallization temperature profiles that are substantially independent of polymer density, elastic modulus and morphology. In a preferred embodiment, the microcrystalline order of the polymer exhibits characteristic constellations and layers distinguishable from random or block copolymers, even at PDI values down to less than 1.7, or even less than 1.5, to less than 1.3.

Moreover, the interpolymers of the present invention can be prepared using techniques to affect the degree or level of blockiness. That is, the amount of comonomer and the length of each polymer block or segment can be varied by controlling the ratio and type of catalyst and transfer agent, as well as the polymerization temperature and other polymerization parameters. A surprising advantage of this phenomenon is the discovery that as the degree of blockiness increases, the optical properties, tear strength and high temperature recovery properties of the polymer obtained are improved. In particular, turbidity decreases as the average number of blocks in the polymer increases, while transparency, tear strength and high temperature recovery properties increase. By selecting a transfer agent and catalyst combination with the desired chain transfer capacity (high rate of movement with low levels of chain termination), other forms of polymer termination are effectively suppressed. Thus, even if very little β-hydride removal is observed in the polymerization of the ethylene / α-olefin comonomer mixtures according to embodiments of the invention, the crystalline blocks obtained are highly or substantially completely, with little or no long chain branching. It is not linear.

 Polymers with highly crystalline chain ends can be optionally prepared according to embodiments of the present invention. In elastomer applications, reducing the relative amount of polymer terminated with amorphous blocks reduces the intermolecular dilution effect on the crystalline region. The above results can be obtained by selecting chain transfer agents and catalysts having an appropriate reaction with hydrogen or other chain terminators. Specifically, catalysts that produce highly crystalline polymers are more likely to have chain terminations than catalysts (e.g., by higher comonomer incorporation, regio-errors, or atactic polymer formation) that contribute to producing less crystalline polymer segments. If more sensitive (eg, with hydrogen), the highly crystalline polymer segment will predominantly be located at the terminal portion of the polymer. Not only are the end groups obtained crystalline, but upon termination, the highly crystalline polymer forming catalyst site can once again be used to resume polymer formation. The initially formed polymer is therefore another highly crystalline polymer segment. Thus, both ends of the multi-block copolymers obtained are mainly very crystalline.

The ethylene α-olefin interpolymers used in the embodiments of the present invention are preferably interpolymers of ethylene and at least one C ₃ -C ₂₀ α-olefin. Particular preference is given to copolymers of ethylene and C ₃ -C ₂₀ α-olefins. The interpolymer may further comprise a C ₄ -C ₁₈ diolefin and / or alkenylbenzene. Suitable unsaturated comonomers useful for polymerizing with ethylene include, for example, ethylenically unsaturated monomers, conjugated or nonconjugated dienes, polyenes, alkenylbenzenes and the like. Examples of such comonomers are C such as propylene, isobutylene, 1-butene, 1-hexene, 1-pentene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene and the like. ₃ -C ₂₀ α-olefins. Particular preference is given to 1-butene and 1-octene. Other suitable monomers include styrene, halo or alkyl-substituted styrenes, vinylbenzocyclobutane, 1,4-hexadiene, 1,7-octadiene and naphthenic materials (eg cyclopentene, cyclohexene and cyclooctene) do.

Ethylene / α-olefin interpolymers are preferred polymers, but other ethylene / olefin polymers may be used. Olefin as used herein refers to a class of unsaturated hydrocarbon-based compounds having one or more carbon-carbon double bonds. Depending on the choice of catalyst, any olefin can be used in embodiments of the present invention. Preferably, suitable olefins are C ₃ -C ₂₀ aliphatic and aromatic compounds containing vinylic unsaturations, as well as cyclic compounds such as cyclobutene, cyclopentene, dicyclopentadiene, and the 5 and 6 positions are C ₁ Norbornene, including but not limited to norbornene substituted with a -C ₂₀ hydrocarbyl or cyclohydrocarbyl group. Mixtures of the olefins as well as mixtures of the olefins with C ₄ -C ₄₀ diolefin compounds are included.

Examples of olefin monomers include propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 4,6-dimethyl-1-heptene, 4 Vinylcyclohexene, vinylcyclohexane, norbornadiene, ethylene norbornene, cyclopentene, cyclohexene, dicyclopentadiene, cyclooctene, and 1,3-butadiene, 1,3-pentadiene, 1,4-hexa Includes, but is not limited to, C ₄ -C ₄₀ dienes, other C ₄ -C ₄₀ α-olefins, including, but not limited to, dienes, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene do. In certain embodiments, the α-olefin is propylene, 1-butene, 1-pentene, 1-hexene, 1-octene or a combination thereof. Although any hydrocarbon containing vinyl groups can potentially be used in embodiments of the present invention, practical problems such as monomer availability, unit cost, and the ability to conveniently remove unreacted monomers from the resulting polymers lead to higher molecular weights of the monomers. This can be more problematic.

The polymerization process described herein is suitable for the preparation of olefin polymers comprising monovinylidene aromatic monomers including styrene, o-methyl styrene, p-methyl styrene, t-butylstyrene and the like. In particular, interpolymers comprising ethylene and styrene can be prepared according to the teachings herein. Optionally, copolymers comprising C ₃ -C ₂₀ α-olefins, including ethylene, styrene and optionally C ₄ -C ₂₀ dienes, with improved properties can be prepared.

Suitable nonconjugated diene monomers may be straight, branched or cyclic hydrocarbon dienes having 6 to 15 carbon atoms. Examples of suitable nonconjugated dienes include linear acyclic dienes such as 1,4-hexadiene, 1,6-octadiene, 1,7-octadiene, 1,9-decadiene, 5-methyl-1,4-hexa Dienes; 3,7-dimethyl-1,6-octadiene; Branched chain acyclic dienes, 1,3-cyclopentadiene, such as 3,7-dimethyl-1,7-octadiene and mixed isomers of dihydromyriene and dihydroocene; 1,4-cyclohexadiene; Monocyclic alicyclic dienes such as 1,5-cyclooctadiene and 1,5-cyclododecadiene, and tetrahydroindene, methyl tetrahydroindene, dicyclopentadiene, bicyclo- (2,2,1 Polycyclic alicyclic fusions and bridged ring dienes such as) -hepta-2,5-diene; 5-methylene-2-norbornene (MNB); 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5- (4-cyclopentenyl) -2-norbornene, 5-cyclohexylidene-2-norbornene, 5- Alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornene, such as vinyl-2-norbornene and norbornadiene. Among the dienes typically used to prepare EPDM, particularly preferred dienes are 1,4-hexadiene (HD), 5-ethylidene-2-norbornene (ENB), 5-vinylidene-2-norbornene (VNB ), 5-methylene-2-norbornene (MNB), and dicyclopentadiene (DCPD). Particularly preferred dienes are 5-ethylidene-2-norbornene (ENB) and 1,4-hexadiene (HD).

One class of preferred polymers that may be prepared according to embodiments of the present invention are elastomeric interpolymers of ethylene, C ₃ -C ₂₀ α-olefins, in particular propylene, and optionally one or more diene monomers. Preferred α-olefins for use in this embodiment of the invention are represented by the formula CH ₂ = CHR ^{* wherein} R ^* is a linear or branched alkyl group having from 1 to 12 carbon atoms. Examples of suitable α-olefins include, but are not limited to, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene and 1-octene. Particularly preferred α-olefins are propylene. Propylene based polymers are generally referred to in the art as EP or EPDM polymers. Suitable dienes for use in preparing such polymers, especially multi-block EPDM type polymers, include conjugated or non-conjugated, straight or branched chain-, cyclic- or polycyclic-dienes comprising 4 to 20 carbons. Preferred dienes include 1,4-pentadiene, 1,4-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, cyclohexadiene, and 5-butylidene-2-norbornene . Particularly preferred dienes are 5-ethylidene-2-norbornene.

Diene-containing polymers contain alternating segments or blocks containing more or less amounts of dienes (including none) and α-olefins (even if they do not), so that subsequent polymer properties are not lost. The total amount of dienes and α-olefins can be reduced without. That is, since dienes and α-olefin monomers are predominantly incorporated into one type of polymer block rather than uniformly or randomly incorporated throughout the polymer, they are used more efficiently, so that the crosslinking density of the polymer is better controlled. Can be. The crosslinkable elastomers and cured articles have advantageous properties including higher tensile strength and better elastic recovery.

In some embodiments, the inventive interpolymers prepared by two catalysts incorporating different amounts of comonomer have a weight ratio of the blocks formed thereby of 95: 5 to 5:95. The elastomeric polymer preferably has 20 to 90% ethylene content, 0.1 to 10% diene content and 10 to 80% α-olefin content based on the total weight of the polymer. More preferably, the multi-block elastomeric polymer has an ethylene content of 60 to 90%, a diene content of 0.1 to 10% and an α-olefin content of 10 to 40% based on the total weight of the polymer. Preferred polymers have a weight average molecular weight (M _w ) of 10,000 to about 2,500,000, preferably 20,000 to 500,000, more preferably 20,000 to 350,000, a polydispersity of less than 3.5, more preferably less than 3.0, Mooney) high molecular weight polymer having a viscosity (ML (1 + 4) 125 ° C.) of 1 to 250. More preferably, such polymers have an ethylene content of 65 to 75%, a diene content of 0 to 6% and an α-olefin content of 20 to 35%.

Ethylene / α-olefin interpolymers can be functionalized by incorporating one or more functional groups into their polymer structure. Examples of functional groups may include, for example, ethylenically unsaturated monofunctional and difunctional carboxylic acids, ethylenically unsaturated monofunctional and difunctional carboxylic anhydrides, salts thereof and esters thereof. Such functional groups may be grafted to ethylene / α-olefin interpolymers or may be copolymerized with ethylene and any additional comonomer to form interpolymers of ethylene, functional comonomers and optionally other comonomer (s). . Means for grafting functional groups on polyethylene are described, for example, in US Pat. Nos. 4,762,890, 4,927,888 and 4,950,541, the disclosures of which are incorporated herein by reference in their entirety. One particularly useful group is maleic anhydride.

The amount of functional groups present in the functional interpolymer can vary. The functional group may typically be present in the copolymerized functionalized interpolymer in an amount of at least about 1.0 wt%, preferably at least about 5 wt%, more preferably at least about 7 wt%. The functional group is typically present in the copolymerized functionalized interpolymer in an amount of less than about 40 weight percent, preferably less than about 30 weight percent, more preferably less than about 25 weight percent.

Additions to the Block Index

The random copolymer satisfies the following relationship. PJ Flory, Trans. Faraday Soc. , 51 , 848 (1955), which is incorporated herein by reference in its entirety.

)의 역함수로서 에틸렌 몰분율의 자연 로그에 대한 관계식과 유사하다.In Equation 1, the mole fraction (P) of the crystalline monomer is associated with the melting temperature (T _m ) of the copolymer and the melting temperature (T _m ⁰ ) of the pure crystalline homopolymer. The above equation is based on the ATREF elution temperature (as shown in FIG. 8 for various homogeneously branched copolymers of ethylene and olefins).

As an inverse of), it is similar to the relationship to the natural logarithm of the ethylene mole fraction.

As illustrated in FIG. 8, the relationship of ethylene mole fraction to DSC melt temperature and ATREF peak elution temperature of various homogeneous branched copolymers is similar to Floris equation. Similarly, preparative TREF fractions of almost all random copolymers and random copolymer blends also fall on the line except for the small molecular weight effect.

According to Flory, the polymer is random when the ethylene mole fraction (P) is equal to the conditional probability that one ethylene unit is before or after another. On the other hand, if the conditional probability that any two ethylene units are present sequentially exceeds P, the copolymer is a block copolymer. The remaining cases where the conditional probability is less than P are alternating copolymers.

The mole fraction of ethylene in the random copolymer primarily determines the specific distribution of the ethylene segments whose crystallization behavior depends on the minimum equilibrium crystal thickness at a given temperature. Thus, the TREF crystallization temperature and the copolymer melting temperature of the block copolymers of the present invention are related to the magnitude of the deviation from the random relationship of FIG. 8, which is such that the "blocking" predetermined TREF fraction is randomly equivalent copolymer (or random) thereof. This is a useful way to quantify how relevant the equivalent TREF fraction is). The term "blocking" refers to the extent to which a particular polymer fraction or polymer comprises a block of polymerized monomers or comonomers. There are two random equivalents (one corresponding to constant temperature and one corresponding to constant ethylene mole fraction). These form the right triangle sides shown in FIG. 9, which illustrates the definition of the block index.

In FIG. 9, points (Tx, Px) represent preparative TREF fractions, where ATREF elution temperature (Tx) and NMR ethylene mole fraction (Px) are measured values. In addition, the ethylene mole fraction (P _AB ) of all the polymers is measured by NMR. The “hard segment” elution temperature and mole fraction (T _A , P _A ) can be calculated or set to the elution temperature and mole fraction of the ethylene homopolymer in the case of ethylene copolymers. The T _AB value corresponds to the random copolymer equivalent ATREF elution temperature calculated based on the measured P _AB . From the measured ATREF elution temperature (T _x ), the corresponding random ethylene mole fraction (P _Xo ) can also be calculated. The square of the block exponent is defined as the area ratio of the (P _x , T _x ) triangle to the (T _A , P _AB ) triangle. Since the right triangles are similar, the area ratio is also the square of the ratio of the distance from (T _A , P _AB ) and (T _x , P _x ) to the random line. In addition, the similarity of the right triangle means that the ratio of the length of either of the corresponding sides can be used instead of the area.

The most complete block distribution would correspond to the entire polymer with a single eluted fraction at point (T _A , P _AB ), which contained all of the soluble octene while maintaining the ethylene segment distribution in the "hard segment" It is assumed that the examples assume almost the same as those produced by the soft segment catalyst). In most cases, "soft segments" do not crystallize in ATREF (or preparative TREF).

The amount of ethylene / α-olefin interpolymers in the polymer blends disclosed herein depends on several factors, such as the type and amount of the two polymers. In general, the amount should be sufficient to be effective as a compatibilizer as described above. In some embodiments, the amount should be an amount sufficient to change the morphology between two polymers in the resulting blend. Typically, the amount is about 0.5 to about 99 weight percent, about 5 to about 95 weight percent, about 10 to about 90 weight percent, about 20 to about 80 weight percent, about 0.5 to about 50 weight percent of the total weight of the polymer blend. , About 50 to about 99 weight percent, about 5 to about 50 weight percent, or about 50 to about 95 weight percent. Preferably the compatibilizer is present in an amount from about 2% to about 15% by weight. In some embodiments, the amount of ethylene / a-olefin interpolymer in the polymer blend is about 1% to about 30%, about 2% to about 20%, about 3% to about 15% by weight of the total polymer blend weight. Or from about 4% to about 10% by weight. In some embodiments, the amount of ethylene / α-olefin interpolymers in the polymer blend is less than about 50 weight percent, less than about 40 weight percent, less than about 30 weight percent, less than about 20 weight percent, less than about 15 weight percent, about 10 weight Less than about, less than about 9 weight percent, less than about 8 weight percent, less than about 7 weight percent, less than about 6 weight percent, less than about 5 weight percent, less than about 4 weight percent, less than about 3 weight percent, less than about 2 weight percent Or less than about 1 weight percent, but greater than about 0.1 weight percent.

polymer

Microporous films comprising the polymer blends disclosed herein may include two or more polymers in addition to the one or more compatibilizers described above. Examples of suitable polymers include thermoplastics, polyolefins, amide based polymers and ethylene-styrene based copolymers. The polymer may be functionalized.

Polyolefins are polymers derived from two or more olefins (ie alkenes). Olefins (ie, alkenes) are hydrocarbons containing at least one carbon-carbon double bond. The olefins are monoenes (ie, olefins with one carbon-carbon double bond), dienes (ie, olefins with two carbon-carbon double bonds), trienes (ie, olefins with three carbon-carbon double bonds) ), Tetraenes (ie olefins with four carbon-carbon double bonds) and other polyenes. Olefins or alkenes such as monoenes, dienes, trienes, tetraenes and other polyenes may have at least 3 carbon atoms, at least 4 carbon atoms, at least 6 carbon atoms, or at least 8 carbon atoms. In some embodiments, the olefin has 3 to about 100 carbon atoms, 4 to about 100 carbon atoms, 6 to about 100 carbon atoms, 8 to about 100 carbon atoms, 3 to about 50 carbon atoms, 3 to about 25 carbon atoms, 4 To carbon number of about 25, carbon number of 6 to about 25, carbon number of 8 to about 25, or carbon number of 3 to about 10. In some embodiments, the olefin is a linear or branched, cyclic or acyclic monoene having 2 to about 20 carbon atoms. In other embodiments, the alkenes are dienes such as butadiene and 1,5-hexadiene. In further embodiments, one or more hydrogen atoms of the alkenes are substituted with alkyl or aryl. In certain embodiments, the alkenes are ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, norbornene, 1-decene, butadiene, 1,5-hexadiene , Styrene or a combination thereof.

The amount of polymer in the polymer blend is about 0.5 to about 99 weight percent, about 10 to about 90 weight percent, about 20 to about 80 weight percent, about 30 to about 70 weight percent, about 5 to about 50 weight of the total weight of the polymer blend. %, About 50 to about 95 weight percent, about 10 to about 50 weight percent, or about 50 to about 90 weight percent. In one embodiment, the amount of polymer in the polymer blend is about 50%, 60%, 70% or 80% based on the total weight of the polymer blend. The weight ratio of the two polyolefins is about 1:99 to about 99: 1, preferably about 5:95 to about 95: 5, about 10:90 to about 90:10, about 20:80 to about 80:20, about 30 : 70 to about 70:30, about 40:60 to about 60:40, about 45:55 to about 55:45 to about 50:50.

Any polyolefin known to those skilled in the art can be used to prepare the polymer blends disclosed herein. The polyolefins can be olefin homopolymers, olefin copolymers, olefin terpolymers, olefin quaternary copolymers, and the like, and combinations thereof. The polyolefin may be a high density or low density polyolefin. "High density" means a density greater than 0.93 g / cc, and "low density" means a density less than 0.93 g / cc. The polyolefin may have a composition distribution width index (CDBI) of greater than 50%, preferably greater than 70%, more preferably greater than 90%. Methods of measuring CDBI and definitions thereof can be found in US Pat. No. 5,246,783, US Pat. No. 5,008,204 and WO93 / 04486, the teachings of which are incorporated herein by reference.

In some embodiments, one of the two or more polyolefins is an olefin homopolymer. The olefin homopolymer can be derived from one olefin. Any olefin homopolymer known to those skilled in the art can be used. Non-limiting examples of olefin homopolymers include polyethylene (eg, ultra low density, low density, linear low density, medium density, high density and ultra high density polyethylene), polypropylene, polybutylene (eg polybutene-1), poly Pentene-1, polyhexene-1, polyoctene-1, polydecene-1, poly-3-methylbutene-1, poly-4-methylpentene-1, polyisoprene, polybutadiene, poly-1,5-hexa Dienes are included. Generally, high density polyethylene (HDPE) has a density greater than 0.94 g / cc, linear low density polyethylene (LLDPE) has a density in the range of 0.92 g / cc to 0.94 g / cc, and low density polyethylene (LDPE) has 0.92 g / cc. has a density of less than cc.

In further embodiments, the olefin homopolymer is polypropylene. Any polypropylene known to those skilled in the art can be used to prepare the polymer blends disclosed herein. Non-limiting examples of polypropylene include low density polypropylene (LDPP), high density polypropylene (HDPP), high melt strength polypropylene (HMS-PP), high impact polypropylene (HIPP), isotactic polypropylene (iPP), syndiotact Tic polypropylene (sPP) and the like, and combinations thereof.

The amount of polypropylene in the polymer blend is about 0.5 to about 99 weight percent, about 10 to about 90 weight percent, about 20 to about 80 weight percent, about 30 to about 70 weight percent, about 5 to about 50 of the total weight of the polymer blend. Weight percent, about 50 to about 95 weight percent, about 10 to about 50 weight percent, or about 50 to about 90 weight percent. In one embodiment, the amount of polypropylene in the polymer blend is about 50%, 60%, 70% or 80% based on the total weight of the polymer blend.

In other embodiments, one of the two or more polyolefins is an olefin copolymer. The olefin copolymer can be derived from two different olefins. The amount of olefin copolymer in the polymer blend is about 0.5 to about 99 weight percent, about 10 to about 90 weight percent, about 20 to about 80 weight percent, about 30 to about 70 weight percent, and about 5 to about the total weight of the polymer blend. 50 weight percent, about 50 to about 95 weight percent, about 10 to about 50 weight percent, or about 50 to about 90 weight percent. In some embodiments, the amount of olefin copolymer in the polymer blend is about 10%, 15%, 20%, 25%, 30%, 35%, 40% or 50% of the total weight of the polymer blend.

Any olefin copolymer known to those skilled in the art can be used in the polymer blends disclosed herein. Non-limiting examples of olefin copolymers include copolymers derived from ethylene and monoenes having at least 3 carbon atoms. Non-limiting examples of monoenes having 3 or more carbon atoms include propene; Butenes (eg 1-butene, 2-butene and isobutene) and alkyl substituted butenes; Pentenes (eg 1-pentene and 2-pentene) and alkyl substituted pentenes (eg 4-methyl-1-pentene); Hexene (eg 1-hexene, 2-hexene and 3-hexene) and alkyl substituted hexene; Heptenes (eg 1-heptene, 2-heptene and 3-heptene) and alkyl substituted heptenes; Octenes (eg 1-octene, 2-octene, 3-octene and 4-octene) and alkyl substituted octenes; Nonene (eg 1-nonene, 2-nonene, 3-nonene and 4-nonene) and alkyl substituted nonene; Decene (eg, 1-decene, 2-decene, 3-decene, 4-decene and 5-decene) and alkyl substituted decene; Dodecene and alkyl substituted dodecene; And butadiene. In some embodiments, the olefin copolymer is an ethylene / alpha-olefin (EAO) copolymer or an ethylene / propylene copolymer (EPM). In some embodiments, the EPM has a melting temperature of at least about 130 ° C. In some embodiments, the olefin copolymer is an ethylene / octene copolymer. In some embodiments, the olefin copolymer is a propylene based polymer.

In other embodiments, the olefin copolymer comprises (i) C _3-20 olefins substituted with alkyl or aryl groups (eg, 4-methyl-1-pentene and styrene), and (ii) dienes (eg, Butadiene, 1,5-hexadiene, 1,7-octadiene and 1,9-decadiene). Non-limiting examples of such olefin copolymers include styrene-butadiene-styrene (SBS) block copolymers.

In other embodiments, one of the two or more polyolefins is an olefin terpolymer. The olefin terpolymer can be derived from three different olefins. The amount of olefin terpolymer in the polymer blend is about 0.5 to about 99 weight percent, about 10 to about 90 weight percent, about 20 to about 80 weight percent, about 30 to about 70 weight percent, and about 5 to about the total weight of the polymer blend. About 50 wt%, about 50 to about 95 wt%, about 10 to about 50 wt%, or about 50 to about 90 wt%.

Any olefin terpolymer known to those skilled in the art may be used in the polymer blends disclosed herein. Non-limiting examples of olefin terpolymers include terpolymers derived from (i) ethylene, (ii) monoene having at least 3 carbon atoms, and (iii) dienes. In some embodiments, the olefin terpolymers are ethylene / alpha-olefin / diene terpolymers (EAODM) and ethylene / propylene / diene terpolymers (EPDM).

In other embodiments, the olefin terpolymer is derived from (i) two different monoenes, and (ii) C _3-20 olefins substituted with alkyl or aryl groups. Non-limiting examples of such olefin terpolymers include styrene-ethylene-co- (butene) -styrene (SEBS) block copolymers.

In other embodiments, one of the two or more polyolefins can be any vulcanizable elastomer or rubber derived from one or more olefins, provided that it can be crosslinked (ie, vulcanized) by a crosslinking agent). Vulcanizable elastomers and thermoplastics such as polypropylene may together form TPV after crosslinking. Vulcanizable elastomers, although generally thermoplastic in the non-cured state, are generally classified as thermosets, since vulcanizable elastomers are irreversible thermosets and become unprocessable. Preferably, the vulcanized elastomer is dispersed in the thermoplastic polymer matrix as a domain. Average domain sizes range from about 0.1 micrometers to about 100 micrometers, from about 1 micrometer to about 50 micrometers, from about 1 micrometer to about 25 micrometers, from about 1 micrometer to about 10 micrometers, or from about 1 micrometer to It may range from about 5 micrometers.

Non-limiting examples of suitable vulcanizable elastomers or rubbers include ethylene / higher alpha-olefin / polyene terpolymer rubbers such as EPDM. Any such terpolymer rubber that can be fully cured (crosslinked) with a phenolic curing agent or other crosslinking agent is sufficient. In some embodiments, the terpolymer rubber is preferably copolymerized with essentially one or more polyenes (ie, alkenes comprising two or more carbon-carbon double bonds), typically non-conjugated dienes and essentially non- Crystalline, rubbery terpolymers of two or more alpha-olefins. Suitable terpolymer rubbers include products derived from the polymerization of two olefins with only one double bond, generally ethylene and propylene, and monomers comprising small amounts of non-conjugated dienes. The amount of non-conjugated diene is typically about 2 to about 10 weight percent of the rubber. Any terpolymer rubber having sufficient reactivity to fully cure with the phenolic curing agent is suitable. The reactivity of the terpolymer rubber varies with both the amount and type of unsaturation present in the polymer. For example, terpolymer rubbers derived from ethylidene norbornene are more reactive to phenolic curing agents than terpolymer rubbers derived from dicyclopentadiene and terpolymers derived from 1,4-hexadiene. Rubbers are less reactive to phenolic curing agents than terpolymer rubbers derived from dicyclopentadiene. However, differences in reactivity can be overcome by polymerizing large amounts of less active dienes into rubber molecules. For example, 2.5% by weight of ethylidene norbornene or dicyclopentadiene may be sufficient to impart sufficient reactivity to the terpolymer to fully cure with phenolic curing agents including conventional curing activators, 3.0 wt% or more is required to achieve sufficient reactivity in the terpolymer rubber derived from 1,4-hexadiene. Terpolymer copolymers of the same grade as EPDM rubbers suitable for embodiments of the invention are commercially available. Some of the EPDM rubbers are disclosed in Rubber World Blue Book 1975 Edition, Materials and Compounding Ingredients for Rubber, pages 406-410.

Generally, terpolymer elastomers have an ethylene content of about 10 wt% to about 90 wt%, a higher alpha-olefin content of about 10 wt% to about 80 wt%, and about 0.5 wt%, based on the total weight of the polymer It has a polyene content of about 20% by weight. Higher alpha-olefins contain about 3 to about 14 carbon atoms. Examples of these are propylene, isobutylene, 1-butene, 1-pentene, 1-octene, 2-ethyl-1-hexene, 1-dodecene and the like. Polyenes include conjugated dienes such as isoprene, butadiene, chloroprene and the like; Nonconjugated dienes; Triene, or higher polyenes of triene or higher. Examples of the triene are 1,4,9-decatene, 5,8-dimethyl-1,4,9-decatene, 4,9-dimethyl-1,4,9-decatene and the like. Nonconjugated dienes are more preferred. Nonconjugated dienes contain 5 to about 25 carbon atoms. Examples include nonconjugated diolefins such as 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 2,5-dimethyl-l, 5-hexadiene, 1,4-octadiene, and the like. ; Cyclic dienes such as cyclopentadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene and the like; Vinyl cyclic enes such as 1-vinyl-1-cyclopentene, 1-vinyl-1-cyclohexene and the like; Alkylbicyclo nondienes such as 3-methyl-bicyclo (4,2,1) nona-3,7-diene, 3-ethylbicyclonondiene and the like; Indenes such as methyl tetrahydroindene and the like; Alkenyl norbornenes such as 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-metalyl-5-norbornene, 2-isopropenyl-5-norbornene, 5- (l, 5-hexadienyl) -2-norbornene, 5- (3,7-octadienyl) -2-norbornene and the like; And tricyclo dienes such as 3-methyl-tricyclo- (5,2, l, 0 ² , 6) -3,8-decadiene and the like.

In some embodiments, the terpolymer rubber has about 20% to about 80% ethylene, about 19% to about 70% higher alpha-olefin, and about 1% to about 10% nonconjugated It contains diene. More preferred higher alpha-olefins are propylene and 1-butene. More preferred polyenes are ethylidene norbornene, 1,4-hexadiene and dicyclopentadiene.

In other embodiments, the terpolymer rubber has an ethylene content of about 50% to about 70% by weight, a propylene content of about 20% to about 49% by weight, and about 1% to about based on the total weight of the polymer Have a non-conjugated diene content of 10% by weight.

Some non-limiting examples of terpolymer rubbers used include NORDEL® IP 4770R, Nordel® 3722 IP (available from The Dow Chemical Company, Midland, Mich.) And Keltan ( KELTAN® 5636A (available from DSM Elastomers Americas, Addis, Louisiana, USA).

Further suitable elastomers are U.S. Patents 4,130,535, 4,111,897, 4,311,628, 4,594,390, 4,645,793, 4,808,643, 4,894,408, 5,936,038, 5,985,970 and 6,277,916 (all 6,277,916). Of which is incorporated herein by reference.

additive

Optionally, the polymer blends disclosed herein may include one or more additives to improve and / or control the processability, appearance, physical properties, chemical properties, and / or mechanical properties of the polymer blends. In some embodiments, the polymer blend does not include an additive. Any plastic additive known to those skilled in the art can be used in the polymer blends disclosed herein. Non-limiting examples of suitable additives include slip agents, antiblocking agents, plasticizers, antioxidants, UV stabilizers, colorants or pigments, fillers, lubricants, invincible agents, flow aids, coupling agents, nucleating agents, surfactants, solvents, flame retardants, antistatic agents And combinations thereof. The total amount of additives is greater than about 0% to about 80%, about 0.001% to about 70%, about 0.01% to about 60%, about 0.1% to about 50%, about 1% to about 40% of the total weight of the polymer blend. Or from about 10% to about 50%. Some polymer additives are described in Zweifel Hans et al. , " Plastics Additives Handbook ," Hanser Gardner Publications, Cincinnati, Ohio, 5th edition (2001).

In some embodiments, the polymer blends disclosed herein comprise a slip agent. In other embodiments, the polymer blends disclosed herein do not include slip agents. Slip is the sliding of the film surfaces onto each other or some other substrate. The slip performance of the film can be measured by ASTM D 1894 ( Static and Kinetic Coefficients of Friction of Plastic Film and Sheeting ) ( incorporated herein by reference). In general, slip agents can be made to have slip properties by changing the surface properties of the film and reducing the friction between the film layers and between the film and other surfaces that the film is in contact with.

Any slip agent known to those skilled in the art can be added to the polymer blends disclosed herein. Non-limiting examples of slip agents include primary amides having about 12 to about 40 carbon atoms (eg, erucamide, oleamide, stearamide, and behenamide); Secondary amides having about 18 to about 80 carbon atoms (eg, stearyl erucamide, behenyl erucamide, methyl erucamide and ethyl erucamide); Secondary-bis-amides having about 18 to about 80 carbon atoms (eg, ethylene-bis-stearamide and ethylene-bis-oleamide); And combinations thereof. In certain embodiments, the slip agent for the polymer blends disclosed herein is an amide of formula (I)

Wherein R ¹ and R ² are each independently H, alkyl, cycloalkyl, alkenyl, cycloalkenyl or aryl; R ³ is alkyl or alkenyl having about 11 to about 39 carbon atoms, about 13 to about 37 carbon atoms, about 15 to about 35 carbon atoms, about 17 to about 33 carbon atoms, or about 19 to about 33 carbon atoms. In some embodiments, R ³ is alkyl or alkenyl having 19 to about 39 carbon atoms. In other embodiments, R ³ is pentadecyl, heptadecyl, nonadecyl, henecosanyl, tricosanyl, pentacosanyl, heptacosanyl, nonacosanyl, hectriacotanyl, tritriacotanyl, nonnatria Cotanyl or combinations thereof. In a further embodiment, R ³ is pentadecenyl, heptadecenyl, nonadesenyl, henecosanenyl, tricosanenyl, pentacosanenyl, heptacosanenyl, nonacosanenyl, gentriacotanenyl, tritriacota Neyl, non-natriactanenyl, or a combination thereof.

In some embodiments, the slip agent is a primary amide (eg, stearamide and behenamide) having a saturated aliphatic group of 18 to about 40 carbon atoms. In other embodiments, the slip agent is a primary amide (eg, erucamide and oleamide) having at least one carbon-carbon double bond and unsaturated aliphatic groups containing 18 to about 40 carbon atoms. In further embodiments, the slip agent is a primary amide having at least 20 carbon atoms. In further embodiments, the slip agent is erucamide, oleamide, stearamide, behenamide, ethylene-bis-stearamide, ethylene-bis-oleamide, stearyl erucamide, behenyl erucamide or combinations thereof to be. In certain embodiments, the slip agent is erucamide. In a further embodiment, ATMER ™ (Uniqema, Everberg, Belgium); ARMOSLIP (registered trademark) (Akzo Nobel Polymer Chemicals, Chicago, Illinois); KEMAMIDE (registered trademark) (Witco, Greenwich, Connecticut); And slip agents having commercial names such as CRODAMIDE (registered trademark) (Croda, Edison, NJ). If used, the amount of slip agent in the polymer blend is greater than about 0 to about 3 weight percent, about 0.0001 to about 2 weight percent, about 0.001 to about 1 weight percent, about 0.001 to about 0.5 weight percent, of the total weight of the polymer blend, Or from about 0.05 to about 0.25 weight percent. Some slip agents are described in Zweifel Hans et al. , " Plastic Additives Handbook ," Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 8, pages 601-608 (2001).

Optionally, the polymer blends disclosed herein may include antiblocking agents. In some embodiments, the polymer blends disclosed herein do not include an antiblocking agent. In particular, antiblocking agents can be used to prevent undesired adhesion between contact layers of articles made from polymer blends, especially under mild pressure and heating during storage, manufacture or use. Any antiblocking agent known to those skilled in the art can be added to the polymer blends disclosed herein. Non-limiting examples of antiblocking agents include minerals (e.g., clay, chalk and calcium carbonate), synthetic silica gels (e.g., SYLOBLOC®) (Grace, Columbia, MD, USA) Davison)), natural silica (e.g. SUPER FLOSS, registered trademark) (Celite Corporation, Santa Barbara, CA), talc (e.g. OPTIBLOC, Registered trademarks) (Luzenac, Centennial, Colorado, USA), zeolites (e.g., SIPERNAT, registered trademark) (Degussa, Parsippany, NJ), Alumino Silicates (e.g. SILTON, registered trademark) (Mizusawa Industrial Chemicals, Tokyo, Japan), limestone (e.g., CARBOREX, registered trademark, Georgia, USA Atlanta Omya of ash, spherical polymer particles (e.g., EPOSTAR®, poly (methyl methacrylate) particles (Nippon Shokubai, Tokyo, Japan) and TOSPEARL , Registered particles), silicone particles (GE Silicones, Wilton, CT), waxes, amides (e.g. erucamide, oleamide, stearamide, behenamide, ethylene-bis-stearicamide) , Ethylene-bis-oleamide, stearyl erucamide and other slip agents), molecular sieves, and combinations thereof Mineral particles can lower blocking by creating physical gaps between articles, while organic blocking The inhibitor can migrate to the surface to limit the surface adhesion.When used, the amount of antiblocking agent in the polymer blend is from about 0 to about 3 weight percent, about 0.0001, of the total weight of the polymer blend. About 2% by weight may be, about 0.001 to about 1% by weight, or from about 0.001 to about 0.5% by weight. Some antiblocking agents are described in Zweifel Hans et al. , " Plastic Additives Handbook ," Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 7, pages 585-600 (2001).

Optionally, the polymer blends disclosed herein can include a plasticizer. However, in some embodiments, the polymer blends disclosed herein do not include a plasticizer. Generally, plasticizers are chemicals that can increase the flexibility and lower the glass transition temperature of the polymer. Any plasticizer known to those skilled in the art can be added to the polymer blends disclosed herein. Non-limiting examples of plasticizers include abietates, adipates, alkyl sulfonates, azelates, benzoates, chlorinated paraffins, citrate, epoxides, glycol ethers and esters thereof, glutarates, hydrocarbon oils, isobutyrates, oleates , Pentaerythritol derivatives, phosphates, phthalates, esters, polybutenes, ricinoleates, sebacates, sulfonamides, tri- and pyromellitates, biphenyl derivatives, stearates, difuran diesters, fluorine-containing plasticizers, hydrides Oxybenzoic acid esters, isocyanate adducts, multi-cyclic aromatic compounds, natural product derivatives, nitriles, siloxane-based plasticizers, tar-based products, thioethers, and combinations thereof. When used, the amount of plasticizer in the polymer blend can be greater than 0 to about 15 weight percent, about 0.5 to about 10 weight percent, or about 1 to about 5 weight percent of the total weight of the polymer blend. Some plasticizers are described in George Wypych, " Handbook of Plasticizers " ChemTec Publishing, Toronto-Scarborough, Ontario (2004). Films made from these blends can be made into porous films by selectively removing plasticizers using a suitable solvent. Alternatively, phase separated materials or additives may be added in the blend so that the additive or material phase separates when the film is prepared and subsequently cooled to create porosity.

In some embodiments, the polymer blends disclosed herein optionally include antioxidants that can prevent oxidation of the polymer component and organic additives in the polymer blend. Any antioxidant known to those skilled in the art can be added to the polymer blends disclosed herein. Non-limiting examples of suitable antioxidants include aromatic or hindered amines such as alkyl diphenylamines, phenyl-α-naphthylamines, alkyl or aralkyl substituted phenyl-α-naphthylamines, alkylated p-phenylene diamines, tetra Methyl-diaminodiphenylamine and the like; Phenols such as 2,6-di-t-butyl-4-methylphenol; 1,3,5-trimethyl-2,4,6-tris (3 ', 5'-di-t-butyl-4'-hydroxybenzyl) benzene; Tetrakis [(methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane (e.g. Irganox® 1010 (Ciba Geigy, NY, USA) Acryloyl modified phenol; octadecyl-3,5-di-t-butyl-4-hydroxycinnamate (e.g. Irganox® 1076 (commercially available from Ciba-Geigi) Phosphite and phosphonite; hydroxylamine; benzofuranone derivatives; and combinations thereof, if used, the amount of antioxidant in the polymer blend is greater than about 0 to about 5 weight of the total weight of the polymer blend. %, About 0.0001 to about 2.5 weight percent, about 0.001 to about 1 weight percent, or about 0.001 to about 0.5 weight percent Some antioxidants are described in Zweifel Hans et al. , " Plastics Additives Handbook , "Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 1, pages 1- 140 (2001).

In other embodiments, the polymer blends disclosed herein optionally include UV stabilizers that can prevent or reduce degradation of the polymer blend by UV irradiation. Any UV stabilizer known to those skilled in the art can be added to the polymer blends disclosed herein. Non-limiting examples of suitable UV stabilizers include benzophenone, benzotriazole, aryl esters, oxanilides, acrylic esters, formamidine, carbon black, hindered amines, nickel quenchers, hindered amines, phenolic Antioxidants, metal salts, zinc compounds and combinations thereof. If used, the amount of UV stabilizer in the polymer blend is greater than about 0 to about 5 weight percent, about 0.01 to about 3 weight percent, about 0.1 to about 2 weight percent, or about 0.1 to about 1 weight of the total weight of the polymer blend. May be%. Some UV stabilizers are described in Zweifel Hans et al. , " Plastics Additives Handbook " Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 2, pages 141-426 (2001).

In further embodiments, the polymer blends disclosed herein optionally include colorants or pigments that can change the appearance of the polymer blend with the human eye. Any colorant or pigment known to those skilled in the art can be added to the polymer blends disclosed herein. Non-limiting examples of suitable colorants or pigments are inorganic pigments such as metal oxides such as iron oxide, zinc oxide and titanium dioxide, mixed metal oxides, carbon black, organic pigments such as anthraquinones, anthrones, azo and monoazo compounds, arylamides , Benzimidazolone, BONA lake, diketopyrrolo-pyrrole, dioxazine, disazo compound, diarylide compound, flavantron, indanthrone, isoindolinone, isoindolin, metal complex, monoazo salt, Naphthol, b-naphthol, naphthol AS, naphthol lake, perylene, perinone, phthalocyanine, pyrantrone, quinacridone and quinophthalone and combinations thereof. When used, the amount of colorant or pigment in the polymer blend can be greater than about 0 to about 10 weight percent, about 0.1 to about 5 weight percent, or about 0.25 to about 2 weight percent of the total weight of the polymer blend. Some colorants are described in Zweifel Hans et al. , " Plastics Addtivies Handbook " Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 15, pages 813-882 (2001).

Optionally, the polymer blends disclosed herein can include fillers that can be used to specifically control volume, porosity, weight, unit cost, and / or technical performance. Any filler known to those skilled in the art can be added to the polymer blends disclosed herein. Non-limiting examples of suitable fillers include talc, calcium carbonate, chalk, calcium sulfate, clay, kaolin, silica, glass, fumed silica, mica, wollastonite, feldspar, aluminum silicate, calcium silicate, alumina, hydrated alumina such as alumina trihydrate, Glass microspheres, ceramic microspheres, thermoplastic microspheres, barite, wood powder, glass fibers, carbon fiber, marble dust, cement dust, magnesium oxide, magnesium hydroxide, antimony oxide, zinc oxide, barium sulfate, titanium dioxide, titanate and Combinations thereof. In some embodiments, the filler is barium sulfate, talc, calcium carbonate, silica, glass, glass fiber, alumina, titanium dioxide, or mixtures thereof. In other embodiments, the filler is talc, calcium carbonate, barium sulfate, glass fibers or mixtures thereof. If used, the amount of filler in the polymer blend is greater than about 0 to about 80 weight percent, about 0.1 to about 60 weight percent, about 0.5 to about 40 weight percent, about 1 to about 30 weight percent, or the total weight of the polymer blend, or About 10 to about 40 weight percent. Some fillers are described in US Pat. No. 6,103,803 and Zweifel Hans et al. , " Plastics Additives Handbook " Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 17, pages 901-948 (2001), all of which are incorporated herein by reference. The filler may be etched in the composition using a suitable solvent or acid to produce a porous structure.

Optionally, the polymer blends disclosed herein can include a lubricant. In general, lubricants can be used, particularly in the process of producing microporous films. Any lubricant known to those skilled in the art can be added to the polymer blends disclosed herein. Non-limiting examples of suitable lubricants include fatty alcohols and their dicarboxylic acid esters, fatty acid esters of short chain alcohols, fatty acids, fatty acid amides, metal soaps, oligomeric fatty acid esters, fatty acid esters of long chain alcohols, montan waxes, polyethylene waxes, polypropylene waxes Natural and synthetic paraffin waxes, fluoropolymers, and combinations thereof. If used, the amount of lubricant in the polymer blend may be greater than about 0 to about 5 weight percent, about 0.1 to about 4 weight percent, or about 0.1 to about 3 weight percent of the total weight of the polymer blend. Some suitable lubricants are described in Zweifel Hans et al. , " Plastic Additives Handbook ," Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 5, pages 511-552 (2001).

Optionally, the polymer blends disclosed herein can include an antistatic agent. In general, antistatic agents can increase the conductivity of the polymer blend to prevent static charge accumulation. Any antistatic agent known to those skilled in the art can be added to the polymer blends disclosed herein. Non-limiting examples of suitable antistatic agents include conductive fillers (eg carbon black, metal particles and other conductive particles), fatty acid esters (eg glycerol monostearate), ethoxylated alkylamines, diethanolamides, ethoxylated Alcohols, alkylsulfonates, alkylphosphates, quaternary ammonium salts, alkylbetaines and combinations thereof. If used, the amount of antistatic agent in the polymer blend may be greater than about 0 to about 5 weight percent, about 0.01 to about 3 weight percent, or about 0.1 to about 2 weight percent of the total weight of the polymer blend. Some suitable antistatic agents are described in Zweifel Hans et al. , " Plastics Additives Handbook " Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 10, pages 627-646 (2001).

Preparation of Polymer Blends

The components of the polymer blend, ie the two polymers and the compatibilizers and optionally the additives, can be prepared using methods known to those skilled in the art, preferably using a method capable of providing a substantially homogeneous distribution of compatibilizers and / or additives in the polymer. It can be mixed or blended. Non-limiting examples of suitable blending methods include melt blending, solvent blending, extrusion, and the like.

In some embodiments, the components of the polymer blend can be melt blended by a method as described in US Pat. No. 4,152,189 (Guerin et al.). First, all solvents, if present, are heated to an appropriate elevated temperature of about 100 ° C. to about 200 ° C., or about 150 ° C. to about 175 ° C. at a pressure of about 5 torr (667 Pa) to about 10 torr (1333 Pa). Remove from the The ingredients are then weighed into the container at the desired ratio and the polymer contents are formed by heating the container contents in a molten state with stirring.

In other embodiments, the components of the polymer blend are processed using solvent blending. First, the components of the desired polymer blend are dissolved in a suitable solvent and then the mixture is mixed or blended. The solvent is then provided to obtain a polymer blend.

In further embodiments, a physical blending device that provides for dispersive mixing, dispensing mixing, or a combination of dispersing and dispensing mixing may be useful for making homogeneous blends. Both batch and continuous physical blending methods can be used. A non-limiting example of a batch method is a branded blender (BRABENDER®) mixing equipment (e.g., BRABENDER PREP Center (registered trademark) (C. W. Brae, South Huckken, NJ). Bender Instruments, Inc. (available from CW Brabender Instruments, Inc.) or Banbury (registered trademark) internal mixing and roll milling equipment (available from Farrel Company, Ansonia, Connecticut). Non-limiting examples of continuous methods include single screw extrusion, twin screw extrusion, disk extrusion, reciprocating single screw extrusion, and pin barrel single screw extrusion In some embodiments, the additive is ethylene During the extrusion of the / α-olefin interpolymers, polyolefins or polymer blends to be added to the extruder via a feed hopper or feed throat Mixing or blending of polymers by extrusion is described in C. Rauwendaal, " Polymer Extrusion ", Hanser Publishers, New York, NY, pages 322-334 (1986), incorporated herein by reference.

If one or more additives are required in the polymer blend, the desired amount of additives may be added to the polymer, compatibilizer or polymer blend all at once or in portions. In addition, the addition may be carried out in any order. In some embodiments, the additive is first added, mixed or blended with the compatibilizer, and then the additive-containing compatibilizer is blended with the polymer. In other embodiments, the additive is added first, followed by mixing or blending with the polymer followed by the compatibilizer. In a further embodiment, the compatibilizer is first blended with the polymer and then the additive is blended with the polymer blend.

Alternatively, master batches containing high concentrations of additives can be used. In general, master batches can be prepared by blending either a compatibilizer, or a polymer or polymer blend with a high concentration of additives. The master batch may have an additive concentration of about 1 to about 50 weight percent, about 1 to about 40 weight percent, about 1 to about 30 weight percent, or about 1 to about 20 weight percent of the total weight of the polymer blend. The master batch can then be added to the polymer blend in an amount determined to provide the desired additive concentration in the final product. In some embodiments, the master batch is a slip agent, antiblocking agent, plasticizer, antioxidant, UV stabilizer, colorant or pigment, filler, lubricant, invincible, flow aid, coupling agent, nucleating agent, surfactant, solvent, flame retardant, electrostatic It contains an inhibitor or a combination thereof. In other embodiments, the master batch contains a slip agent, antiblocking agent or a combination thereof. In other embodiments, the master batch contains a slip agent.

In some embodiments, the first polymer and the second polymer constitute thermoplastic vulcanization, wherein the first polymer is a thermoplastic such as polypropylene and the second polymer is a curable vulcanizable rubber such as EPDM. Thermoplastic vulcanizates are typically prepared by blending thermoplastics and curable vulcanizable rubbers by dynamic vulcanization. The composition may be prepared by any method suitable for mixing rubbery polymers, including mixing on an internal mixer or on a rubber mill, such as a Banbury mixer. In the compounding procedure, one or more additives described above may be incorporated. In general, it is preferred to add the crosslinking agent or curing agent in a second compounding step, which may be present in an internal mixer or on a rubber mill, usually operating at temperatures below about 60 ° C.

Dynamic vulcanization is the process of masticating a blend of thermoplastics and rubber and rubber hardener while curing the rubber. The term "dynamic" refers to the application of shear force to the mixture during the vulcanization step, as opposed to "static" vulcanization in which the vulcanizable composition is fixed in a fixed relative space during the vulcanization step. One advantage of dynamic vulcanization is that elastoplastic (thermoplastic elastomer) compositions can be obtained when the blend contains a suitable proportion of plastics and rubber. Examples of dynamic vulcanization are U.S. Pat. 4,288,570, 4,299,931, 4,311,628 and 4,338,413, all of which are incorporated herein by reference in their entirety.

Any mixer capable of producing a shear rate of at least 2000 seconds ⁻¹ is suitable for carrying out the process. In general, this requires a high speed internal mixer with a narrow gap between the wall and the tip of the kneading member. Shear velocity is the velocity gradient in the space between the tip and the wall. Depending on the spacing between the tip and the wall, a kneading member rotation of generally about 100 to about 500 rpm is suitable to produce a sufficient shear rate. Depending on the number of tips on the kneading member and the speed of rotation, the number of times the composition is kneaded by each member is about 1 to about 30 times per second, preferably about 5 to about 30 times per second, more preferably Is about 10 to about 30 times per second. This typically means that the material is kneaded about 200 to about 1800 times during vulcanization. For example, in a typical process using a rotor with three tips rotating at about 400 rpm in a mixer having a residence time of about 30 seconds, the material is kneaded about 600 times.

Preferred mixers for carrying out the process are high shear mixed extruders produced by Werner & Pfleiderer, Germany. The Werner and Flyderer (W & P) extruder is a twin-shaft screw extruder in which two interlocking screws rotate in the same direction. Details of such extruders are described in US Pat. Nos. 3,963,679 and 4,250,292, and German Patents 2,302,546, 2,473,764 and 2,549,372, the disclosures of which are incorporated herein by reference. Screw diameters vary from about 53 mm to about 300 mm; Barrel lengths vary but generally the maximum barrel length is the length needed to maintain a constant length at a diameter ratio of about 42. The shaft screws of these extruders are typically composed of a series of transfer zones and kneading zones alternately. The transfer zone advances the material from each kneading zone of the extruder. Typically, approximately the same number of transfer zones and kneading zones are fairly evenly distributed along the barrel length. Kneading members containing one, two, three or four tips are suitable, but a kneading member of about 5 to about 30 mm width with three tips is preferred. At recommended screw speeds of about 100 to about 600 rpm and radial intervals of about 0.1 to about 0.4 mm, the mixing extruder has a shear rate of at least about 2000 seconds ^{-1 to at} least about 7500 seconds ^-1 . The net mixed power consumed in the process, including homogenization and dynamic vulcanization, is typically about 100 to about 500 watt hours per kg of product, and typically about 300 to about 400 watt hours per kg.

The process is illustrated by the use of a W & P twin screw extruder model ZSK-53 or ZSK-83. Unless otherwise specified, all plastics, rubbers and other compounding components except the curing activator are fed to the inlet port of the extruder. In the first third of the extruder, the composition is masticated to melt the plastic and form an essentially homogeneous blend. A cure activator (vulcanization accelerator) is added through another entry port located about one third of the barrel downstream length from the initial entry port. The last two thirds of the extruder (from the curing activator entry port to the extruder outlet) are considered as the dynamic vulcanization zone. An exhaust vent operated under reduced pressure is located near the outlet to remove any volatile byproducts. Occasionally, additional extender oils or plasticizers and colorants are added at another entry port located approximately in the middle of the vulcanization zone.

The residence time in the vulcanization zone is the time during which a certain amount of material is in the vulcanization zone. Since the extruder is typically operated under starved conditions, typically about 60 to about 80% has a residence time essentially proportional to the feed rate. Thus, the residence time in the vulcanization zone is calculated by multiplying the total volume of the dynamic vulcanization zone by the filling factor and dividing it by the volume flow rate. The shear rate is calculated by dividing the product of the circumference of the circle produced by the screw tip with the number of revolutions per second of the screw by the tip spacing. In other words, the shear rate is the tip velocity divided by the tip spacing.

Methods other than the dynamic curing of the rubber / thermoplastic polymer resin blend can be used to prepare the composition. For example, the rubber can be fully cured, powdered, and dynamic in the absence of the thermoplastic polymer resin, and mixed with the thermoplastic polymer resin at temperatures above the melting or softening point of the resin. When the crosslinked rubber particles are small and well dispersed at an appropriate concentration, the composition is easily obtained by blending the crosslinked rubber with the thermoplastic polymer resin. It is desirable to obtain a mixture comprising well dispersed small crosslinked rubber particles. Mixtures containing insufficiently dispersed or too large rubber particles may be ground by cold milling to reduce the particle size to less than about 50 μ, preferably less than about 20 μ, more preferably less than about 5 μ. After sufficient grinding or grinding, a TPV composition is obtained. Often, insufficient dispersion or excessively large rubber particles are visually vivid and observable in the molded sheet. This is especially true in the absence of pigments and fillers. In this case, fine powder and reshaping result in a sheet in which rubber particle aggregates or large particles are not visually clear or much less sharp and the mechanical properties are significantly improved.

Microporous film

Microporous films of the present invention include, but are not limited to, WO2005 / 001956A2, WO2003 / 100954A2, US 6,586,138, US 6,524,742, US 2006/0188786, US 2006/0177643, US 6,749,961, US 6,372,379, and WO 2000 / 34384A1 (all of them) May be used in any of the processes or articles described in this disclosure.

Microporous films of the invention include battery separators, fuel cell materials, condenser separators, diagnostic test kits, wound dressings, HEPA filtration, drug-abuse tests, one-Northern blots, Southern blots, It can be used in articles such as clean-room garments, hydroponic farming, transdermal patches, spiral winding modules, plasma exports, drapes and gown fabrics, medical packaging materials, affinity / chromatography, ion exchangers and ion selectors. Microporous membranes can be formed with geometries such as planar sheet membranes, hollow fiber membranes and tubular membranes.

Microporous films can range from about 0.01 micrometers to about 20 micrometers, from about 0.015 micrometers to about 15 micrometers, from about 0.02 micrometers to about 10 micrometers, and from about 0.04 micrometers to about 0.5 micrometers. It may include pores having a size.

In some embodiments, the microporous film has a thickness of about 5 micrometers to about 200 micrometers, about 5 micrometers to about 24 micrometers, about 10 micrometers to about 40 micrometers, and about 15 micrometers to about 60 micrometers. It may have an average thickness.

In addition, the microporous film may have a thickness of less than about 60 micrometers, less than about 50 micrometers, or less than about 40 micrometers. In some embodiments, the first or second polymer comprises a blend of ethylene based polymers and includes about 50% to about 99%, about 60% to about 95%, and about 65% to about 90% by weight Present in an amount of%.

In some embodiments, the first or second polymer comprises a propylene based polymer. The propylene based polymer may be present in an amount of about 5% to about 50%, about 10% to about 45%, and about 15% to about 35% by weight.

In some embodiments, the microporous film comprises a blend of medium molecular weight high density polyethylene polymer and polyethylene wax. The blend may comprise at least 20 wt%, at least 30 wt%, or at least 50 wt% wax, based on the weight of the blend.

In some embodiments, the microporous film can include additional layers. The additional layer may have the same, similar or different porosity as the one or more layers. The layers can be stacked. They can be laminated to the nonwoven layer. In some embodiments, the microporous film comprises a ceramic layer and / or a heat resistant layer.

Moreover, this invention relates to the separator containing the microporous film of this invention, and the article containing the microporous film of this invention.

In some embodiments, the microporous film has a Gurley value of about 2 seconds / 10 cc to about 80 seconds / 10 cc, about 5 seconds / 10 cc to about 45 seconds / 10 cc, and about 10 seconds / 10 cc to about 40 seconds / lOcc.

The invention also relates to an article comprising the microporous film of the invention. Articles include, but are not limited to, items such as coating membranes, multilayer structures, batteries, filter media, and proton exchange membranes. The batteries can be, for example, alkaline batteries, lithium ion primary batteries, lead acid batteries and fuel cell batteries.

One method of making the microporous film of the present invention comprises the steps of blending a filler or oil with a starting material comprising a first polymer, a second polymer and a compatibilizer, and removing the filler or oil during the film making process Generating porosity. The method may also include functionalizing the film. In addition, in some embodiments, the starting material may have a polymer content of less than about 50 weight percent based on the weight of the starting material and the starting material may comprise more than 60% oil, or up to 95% oil It may comprise, the starting material may comprise a wax.

The invention also includes a microporous film of the invention containing at least 80% by weight of a polymer selected from the group consisting of polypropylene, polyethylene and copolymers thereof and having a transverse tear resistance of at least about 50 kgf / cm ² , A method of making a microporous membrane which is a layer or coextruded multilayer membrane and suitable for use as a battery separator, the method comprising:

Extruding the film precursor by a blown film method at a blow-up ratio of at least 1.5;

Annealing the film precursor; And

Stretching the resulting annealed film precursor to form the microporous membrane

It includes.

The present invention can be used in the following films as described in US Patent Application Publication No. 2006/0177643, which is incorporated herein by reference.

(1) a high density polyethylene copolymer having a melt index (MI) of 0.1 to 100 and an alpha-olefin unit content of at least 3 carbon atoms of 0.1 to 1 mol%; And a blend containing high density polyethylene having a viscosity average molecular weight (Mv) of at least 500000 to 5000000, wherein the blend is a microporous Mv having from 300000 to 4000000 and having an alpha-olefin unit content of at least 3 carbon atoms from 0.01 to 1 mol%. Polyethylene film.

(2) a high density polyethylene copolymer having a melt index (MI) of 0.1 to 100 and an alpha-olefin unit content of 3 or more carbon atoms of 0.1 to 1 mol%; And a blend containing homopolyethylene having an Mv of at least 500000 to 5000000, wherein the blend has a Mv of 300000 to 4000000 and an alpha-olefin unit content of at least 3 carbon atoms of 0.01 to 1 mol%.

 (3) a weight fraction measured by GPC of a component having a molecular weight of 1 million or less, comprising a high density polyethylene copolymer containing an alpha-olefin unit having 3 or more carbon atoms, and a blend containing a high density polyethylene, wherein the weight fraction is 1 to 40%; , Characterized in that the weight fraction measured by GPC of a component having a molecular weight of 10000 or less is 1 to 40%, and the component having a molecular weight of 10000 or less has an alpha -olefin unit content of 3 or more carbon atoms and 0.1 to 1 mol%. Wherein the blend has Mv of 300000 to 4000000 and an alpha-olefin unit content of at least 3 carbon atoms of 0.1 to 1 mol%.

(4) The microporous polyethylene film according to any one of (1) to (3), wherein the alpha-olefin is propylene.

(5) The polyethylene according to any one of the above (1) to (4), wherein the polyethylene having a Mv of 500000 to 5000000 is a blend of two or three selected from the following polyethylene (A), (B) and (C): Microporous Polyethylene Film:

(A) the polyethylene described above having an Mv of at least 1500000 and less than 5000000; (B) the polyethylene described above having an Mv of at least 600000 and less than 1500000; And (C) the polyethylene described above wherein Mv is greater than or equal to 250000 and less than 600000.

(6) The microporous polyethylene film according to any one of (1) to (4), wherein the polyethylene described above having Mv of 500000 to 5000000 is an ultrahigh molecular weight polyethylene having Mv of 1500000 or more.

(7) The microporous polyethylene film according to any one of (1) to (6), having a film rupture temperature of 150 ° C or higher.

(8) The microporous polyethylene film according to any one of (1) to (7), wherein the shrinkage force at 150 ° C is 2 N or less.

(9) The microporous polyethylene film according to any one of (1) to (8), which has a fusion temperature of 140 ° C or lower.

(10) The microporous polyethylene film according to any one of (1) to (9), having a thickness of 5 to 200 µm.

(11) The microporous polyethylene film according to any one of (1) to (10), having a porosity of 30 to 70%.

(12) The microporous polyethylene film according to any one of (1) to (11), having an air permeability of 100 seconds or more and 600 seconds or less.

(13) A battery separator comprising the microporous film according to any one of (1) to (12).

The microporous film of the present invention is excellent in mechanical strength, permeability and productivity, has a low fusion temperature and high heat resistance, and is preferable as a battery separator.

The film forming method is not limited to any particular method. For example, mixed polyethylene powder is fed to an extruder in the presence or absence of a plasticizer; Melt kneading both materials at about 200 ° C .; By casting the kneaded material into a chill roll in a conventional coat-hanger die, a sheet having a thickness of several tens of micrometers to several mm can be continuously formed. It is also possible to use an expansion method. The method of supplying the raw material and the plasticizer in the above-described process may be any known method of supplying the resin and the plasticizer in a completely dissolved state or in a slurry state. From the viewpoint of productivity, it is preferable to feed the resin into the extruder in the feed hopper and the plasticizer halfway. In this case, the extruder may have more than one feed opening for feeding the plasticizer.

In addition, as described in US Pat. No. 7,141,168, which is incorporated herein by reference, porous plastic membranes may be used for separation membranes for filtration in medicine and industry, separators in galvanic cells and electrolytic capacitors, linings for paper diapers and other hygiene products. ), And building materials such as construction films and roofing base materials. In particular, porous polyolefin membranes are useful for articles in which the membrane contacts these materials due to their resistance to organic solvents or alkaline or acidic solutions.

The surface of the porous polyolefin film according to the invention can be hydrophilized if necessary, for example by treatment with surfactants, corona discharge, low temperature plasma, sulfonation or UV irradiation, or by grafting under radioactivity. In addition, various coating films may be applied to the surface.

The porous polyolefin films obtained in the processes described above can be used in a variety of articles, such as conventional porous membranes, such as filters and separators for air and water purification, separators for galvanic and electrolytic cells, or moisture-permeable waterproof materials for building materials and clothing.

In addition, the microporous film of the present invention comprises a separator layer located between the anode layer and the cathode layer, as described in US Patent Publication No. 2004/0248012, which is incorporated herein by reference; A separator layer formed of the microporous film of the present invention comprising a polymer matrix comprising a first polyolefin and a second polyolefin, wherein the first polyolefin provides mechanical integrity to the separator layer and the second polyolefin is water-spars to the separator layer. Including reactive functional groups that provide one of scavenging and acid-scavenging properties; And an anode layer and a cathode layer comprising a material composition having electrical conductivity properties.

In addition, as described in US Pat. No. 6,824,680, which is incorporated herein by reference, other components may optionally be included in the blend to change the properties of the microporous film produced herein. For example, the hydrophilicity or hydrophobicity of the film surface traversed by penetration can be changed by including monomers, oligomers, polymers or other compounds in the blend. Such changes may enhance penetration by certain components or phases, or may impede penetration of others. By way of non-limiting example, a surfactant or surface-active agent such as sodium dodecyl sulfate may be included in the blend. By the theory that the Applicant is obliged or not bound by the disclosure, at the microcracked surface, the surface synchronizes with the hydrophobic portion in the matrix and the ionic portion of the surface, increasing the hydrophobicity of the channel or pores throughout the membrane and The permeability to hydrophilic solvents or components in the membrane can be increased, and the permeability to hydrophobic components can be reduced.

The films of the present invention can be used in separation articles comprising solids, liquids, and gases in any combination, used in various fields such as medical, industrial, apparel, food, and packaging articles. Such articles include, but are not limited to, medical applications such as, but not limited to, non-adhesive dressings, burn dressings, and endotracheal tube cuffs; Filtration fields for alkaline battery separators, lead-acid battery separators, bacterial filters, dialysis membranes, industrial or laboratory ultrafiltration supplies, oxygenation supports, reverse osmosis supports and water purification; Industrial degassing articles; Insulation and protective barrier articles including sound absorbing films, mattress ticking, sleeping bag fabrics, tarpaulin, tent fabrics, thermal blankets; Sterile packaging; In the field of disposables for diaper covers, disposable protective clothing, operating room packs and drapes; Clothing sectors such as garment linings, raincoats, shoe linings; Household articles such as travel bags, furniture fabric backings; Tapes, wraps and packaging articles such as agricultural production wraps, cable wraps, capacitor wraps, control-environmental wrappers, industrial tapes, non-fogging wrappers and control-release desiccators for anhydrous fluids. Such uses and articles are merely illustrative non-limiting examples of various articles for the microporous membranes of the present invention.

In addition, the microporous film of the present invention can be used in battery separators as described in US Pat. No. 6,749,961, which is incorporated herein by reference.

The present invention relates to a battery separator comprising a microporous polyolefin membrane made from the microporous film of the present invention having a porosity of 30 to 80% and an average pore size of 0.02 to 2.0 micrometers.

The separator may be a single ply or multi-ply membrane. All separators must have sufficient mechanical strength to withstand the harshness of battery manufacturing and battery use. In addition, the separator must have sufficient thermal stability and shutdown capability. Thermal stability refers to the membrane's ability to maintain its physical dimension substantially during abnormal conditions associated with overheating (eg, allowable shrinkage at elevated temperatures, and the ability to prevent physical contact of the anode and cathode at elevated temperatures). . Shutdown capability refers to the membrane's ability to substantially close the pores through which electrolyte ions conduct current flow between the anode and cathode, as a result of overheating. Shutdown should occur at temperatures below 130 ° C. and should occur rapidly (eg, the width of the temperature response for shutdown is narrow (about 4-5 ° C.)). The microporous membrane preferably has a shutdown temperature of less than about 130 ° C.

In addition, the microporous film of the present invention can be used in battery separators as described in US Pat. No. 6,586,138, which is incorporated herein by reference. Freestanding battery separators include microporous polymer webs having passageways that provide full fluid permeability. The polymeric web preferably comprises a blend of a compatibilizer as described above with UHMWPE and a gel-forming polymeric material. The pattern formed by the gel-forming polymeric material or its structure and the wettability of the UHMWPE polymer web reduces the time required to achieve uniform electrolyte distribution throughout the lithium-ion battery. In a first embodiment, the gel-forming polymeric material is a coating on the UHMWPE web surface. In a second embodiment, the gel-forming polymeric material is incorporated into the UHMWPE web while maintaining overall fluid permeability. Both embodiments produce a hybrid gel electrolyte system in which the gel and the liquid electrolyte coexist.

The present invention also provides a method for manufacturing a nonwoven flat sheet; Providing a microporous membrane; Providing an adhesive solution comprising a solvent, a swellable polymer and a humectant; Coating the sheet or the film or both the sheet and the film with an adhesive solution; Laminating the nonwoven flat sheet and the film; And forming a separator as described in US Pat. No. 7,087,343, which is incorporated herein by reference.

The invention also provides a microporous battery separator having two parts joined together, as described in US Pat. No. 6,921,608, which is incorporated herein by reference. Each part consists of an uncoextruded layer and consists of the same film as the inventive microporous film. In order to obtain a puncture strength greater than one prior art separator, i.e., a multilayer separator of a predetermined thickness, the present invention combines two sized parts together when combined to have the same thickness as the prior art separator. The present invention preferably utilizes a collapsed bubble technique, ie, extrudes a single molten polymer (or blend of polymers) through an annular die and allows bubbles from the die to be discharged from the first and second portions (each portion surrounding the bubble). By a blown film technique, which then collapses the bubbles on their own (preferably by annealing and stretching) and bonds before forming micropores. When the bubble exits the die, the bubble is oriented substantially in the machine direction. Thus, when the bubble collapses and binds on itself, the first and second portions are substantially in the same direction (the angular bias between the oriented portions is less than 15 °), i.e. (US Pat. No. 5,667,911) Orientate without significant angular bias between the first portion and the second portion (as disclosed herein). Disintegration and bonding are performed in the same step by knitting together the melted (or nearly molten) polymer of the bubbles. By bursting and binding the bubbles on their own, an increased puncture strength is obtained at a thickness equivalent to that of the separator of the prior art. The film preferably has a thickness of less than about 1.5 mils, a Gurley value of less than about 50 seconds / 10 cc, and a puncture strength of greater than about 400 g / mil.

As described in EP275027, incorporated herein by reference, the membrane may also include a support layer. Suitable support layers for composite membranes are extensively described in the prior art. Exemplary support materials include organic polymer materials such as polysulfone, polyethersulfone, chlorinated polyvinyl chloride, styrene / acrylonitrile copolymers, polybutylene terephthalate, cellulose esters, and high porosity and controlled pore size distributions. Other polymers that can be prepared are included. In addition, the porous inorganic material may be operable as a support. Preferably, the pores in the polymer will be 1 nanometer to 1,000 nanometers in size, with the widest dimension of the surface in intimate contact with the distinct layer.

The invention may also be used as a separator for lithium polymer batteries as described in US Pat. No. 6,881,515, which is incorporated herein by reference. The separator includes a membrane and a coating. The membrane has a first surface, a second surface, and a plurality of micropores extending from the first surface to the second surface. The coating covers the membrane but does not fill the plurality of micropores. The coating comprises the gel-forming polymer and the plasticizer in a weight ratio of 1: 0.5 to 1: 3.

The invention may also provide a split resistant microporous membrane for use in making battery separators as described in US Pat. No. 6,602,593, which is incorporated herein by reference. The microporous membrane comprises preparing the film precursor by a blown film extrusion process at a blow-up ratio of at least 1.5, annealing the film precursor, and stretching the resulting annealed film precursor to form a microporous membrane. It is manufactured by the process.

The invention also relates to lithium batteries, in particular high energy secondary lithium batteries, and corresponding battery separators as described in US Pat. No. 6,432,586, which is incorporated herein by reference. The separator includes at least one ceramic composite layer and at least one polymeric microporous layer. The ceramic composite layer comprises a mixture of matrix material and inorganic particles. The ceramic composite layer is configured to at least block dendritic growth and prevent electronic short circuits. The polymer layer is configured to block ionic flow between the anode and cathode at least upon overheating.

The invention also relates to a hydrophilic polyolefin article comprising a polyolefin article having a coating containing an ethylene vinyl alcohol (EVOH) copolymer and a surfactant, as described in US Pat. No. 6,287,730, incorporated herein by reference, The polyolefin article comprises the microporous film of the present invention.

In addition, the microporous film of the present invention may be used in any one layer of a battery separator comprising two microporous strength layers interposed with an internal microporous shutdown layer as described in US Pat. No. 6,180,280, which is incorporated herein by reference. Can be. The microporous inner layer is formed by the phase inversion method, while the strength layer is produced by the stretching method. Preferably, the thickness of the three-layer separator is about 2 mils or less, more preferably about 1 mil or less. Preferably, the three layer separator has a shutdown temperature in the range of less than about 124 ° C, more preferably from about 80 ° C to about 120 ° C, even more preferably from about 95 ° C to about 115 ° C. Also provided is a method of making a three-layer shutdown separator. Preferred methods include the steps of (a) extruding a non-porous strength layer precursor; (b) annealing and stretching the non-porous precursor to form a microporous strength layer; (c) extruding the non-porous shutdown layer precursor from the composition comprising the polymer and the extractable material, extracting the extractable material from the precursor to form a microporous structure, and optionally stretching the membrane to orient the microporous membrane. Forming a microporous inner layer by a phase inversion process; And (d) bonding the precursor to a three layer battery separator wherein the first and third layers are strength layers and the second layer is a microporous membrane prepared by a phase inversion method.

The present invention also includes the steps of extruding a parison, as described in US Pat. No. 6,132,654, which is incorporated herein by reference; Disintegrating the parison on itself to form a planar sheet comprising two plies; Annealing the planar sheet; Stretching the planar sheet; And winding a flat sheet, wherein the microporous polyolefin membrane is used in a battery separator having a thickness in the range of about 0.3 mils to about 0.5 mils, wherein the adhesion between the two plies is per inch. Less than 8 g.

Some exemplary embodiments of the invention are as follows:

1. (i) a first polymer;

(ii) a second polymer; And

(iii) an effective amount of a polymer compatibilizer

Microporous film comprising at least one layer comprising a polymer blend comprising.

2. The compound of embodiment 1 wherein (iii) comprises an ethylene / α-olefin interpolymer, wherein the first polymer, the second polymer and the ethylene / α-olefin interpolymer are different and the ethylene / α-olefin interpolymer Films having one or more of the following features:

(a) Mw / Mn of about 1.7 to about 3.5, at least one melting point T _m (° C.), and density d (g / cm ³ ), where the values of T _m and d correspond to the following relationship:

T _m > -2002.9 + 4538.5 (d) -2422.2 (d) ² ); or

(b) a delta value ΔT (° C.), where ΔT, defined as the Mw / Mn of about 1.7 to about 3.5, and the heat of fusion ΔH (J / g), and the temperature difference between the highest DSC peak and the highest CRYSTAF peak The values of and ΔH have the following relationship:

ΔT> -0.1299 (ΔH) + 62.81 (if ΔH is greater than 0 and less than or equal to 130 J / g),

ΔT ≧ 48 ° C. (if ΔH is greater than 130 J / g);

The crisp peak is determined using at least 5% of the cumulative polymer, and if less than 5% of the polymer has an identifiable crisp peak, the crisp temperature is 30 ° C.); or

(c) 300% strain and elastic recovery rate Re (%) at 1 cycle, and density d (g / cm ³ ) measured with a compression-molded film of ethylene / α-olefin interpolymers, wherein the values of Re and d Satisfies the following relationship when the ethylene / α-olefin interpolymer is substantially free of the crosslinked phase:

Re> 1481-1629 (d)); or

(d) molecular fractions eluted at 40 ° C. to 130 ° C. when fractionated using TREF (the fractions having at least 5% higher comonomer molar content than that of the comparative random ethylene interpolymer fractions eluting between the same temperatures) Wherein the comparative random ethylene interpolymer has the same comonomer (s) and has a melt index, density and comonomer molar content (based on total polymer) within 10% of that of the ethylene / α-olefin interpolymers ); or

(e) storage modulus G '(25 ° C.) at 25 ° C., and storage modulus G' (100 ° C.) at 100 ° C., where the ratio of G ′ (25 ° C.) to G ′ (100 ° C.) is about 1: In the range from 1 to about 9: 1); or

(f) at least one molecular fraction characterized by having a block index of at least 0.5 to about 1 and a molecular weight distribution Mw / Mn of greater than about 1.3 and eluting at 40 ° C. to 130 ° C. when fractionated using TREF; or

(g) an average block index greater than 0 and up to about 1.0 and a molecular weight distribution Mw / Mn greater than about 1.3; or

(h) Mw / Mn from about 1.7 to about 3.5, at least one melting point T _m (° C.), and density d (g / cm ³ ), where the values of T _m and d correspond to the following relationship:

T _m > -6553.3 + 13735 (d) -7051.7 (d) ² ).

3. The film of embodiment 1 or 2 wherein (i) and / or (ii) comprises a polyolefin.

4. The film of any of the preceding embodiments, wherein (i) and / or (ii) comprises an olefin homopolymer, an olefin copolymer, an olefin terpolymer, an olefin quaternary copolymer, and the like, and combinations thereof.

5. The film of embodiment 2, wherein the ethylene / α-olefin interpolymer has a weight average molecular weight (Mw) of about 100,000.

6. The film of embodiment 5, wherein the ethylene / α-olefin interpolymer has a weight average molecular weight (Mw) of about 3,000,000 or less.

7. The film of embodiment 5, wherein the ethylene / α-olefin interpolymer has a weight average molecular weight (Mw) of about 10,000 to about 100,000.

8. The film of embodiment 2 wherein the ethylene / α-olefin interpolymer is a diblock copolymer.

9. The film of embodiment 2 wherein the ethylene / α-olefin interpolymer is a triblock copolymer.

10. The film of embodiment 2, wherein the ethylene / α-olefin interpolymer is a multi-block copolymer.

11. The film of embodiment 2, wherein the ethylene / α-olefin interpolymer has a hard segment component in an amount of about 1% to about 99% by weight.

12. The film of embodiment 1 or 2, wherein the first polymer comprises ultra high molecular weight polyethylene having a molecular weight ranging from about 1 million to about 7 million.

13. The film of any preceding embodiment, wherein the polymer is functionalized.

14. The film of any one of the preceding embodiments, wherein the first polymer is a blend of ethylene based polymers and is present in an amount of 50 to 99% by weight.

15. The film of any one of the preceding embodiments, wherein the second polymer is at least one propylene based polymer present in an amount of from 5 to 50 weight.

16. The film of any one of the preceding embodiments, wherein the compatibilizer is present in an amount from 2 to 15 weight percent.

17. The film of any preceding embodiment, wherein the second polymer comprises a propylene based copolymer.

18. The film of embodiment 17, wherein the propylene based copolymer has a melting temperature of at least 130 ° C.

19. The film of any one of the preceding embodiments, wherein the compatibilizer is selected from the group consisting of homogeneously branched linear polyethylene and homogeneously branched substantially linear polyethylene.

20. The film of any preceding embodiment, wherein the compatibilizer is functionalized.

22. The film of any one of the preceding embodiments comprising the functionalized polymer.

23. The film of any one of the preceding embodiments, comprising no plasticizer.

24. The film of any one of the preceding embodiments, wherein the film comprises pores in the range of about 0.02 micrometers to about 10 micrometers.

25. The film of any one of the preceding embodiments, wherein the film comprises pores in the range from about 0.04 micrometers to about 0.5 micrometers.

26. The film of any one of the preceding embodiments, having a Gurley value in the range of about 2 seconds to about 80 seconds.

27. The film of any one of the previous embodiments, having an average thickness in the range of about 5 micrometers to about 200 micrometers.

28. The film of any one of the preceding embodiments having an average thickness in the range of about 5 micrometers to about 24 micrometers.

29. The film of embodiments 1-27, having an average thickness of less than about 40 micrometers.

30. The film of embodiments 1-27, having an average thickness of less than about 25 micrometers.

31. The film of any one of the preceding embodiments, further comprising an additional layer.

32. The film of embodiment 31, wherein the additional layer has the same, similar, or different porosity as the one or more layers.

33. The film of embodiment 31 or embodiment 32 formed by extrusion.

34. The film of any one of embodiments 31 to 33 wherein the layers are laminated.

35. The film of embodiment 34, wherein the layers are laminated to the nonwoven layer.

36. The film of any one of the preceding embodiments, further comprising a ceramic layer.

37. The film of any preceding embodiment, further comprising a heat resistant layer.

38. The compound of any one of embodiments 2 or previous embodiments wherein Mw / Mn, at least one melting point T _m (° C.), and a density d (g / cm ³ ) of about 1.7 to about 3.5, wherein T _m and d The figures correspond to the following relations:

A microporous film comprising an ethylene / α-olefin interpolymer having T _m ≧ 858.91-1825.3 (d) + 1112.8 (d) ² ).

39. The method according to any one of embodiments 2 or previous embodiments, having a Mw / Mn of about 1.7 to about 3.5, and a heat of fusion ΔH (J / g), and the temperature between the highest DSC peak and the highest CRYSTAF peak The delta value ΔT (° C), defined as the difference, where the values of ΔT and ΔH have the following relationship:

ΔT> -0.1299 (ΔH) + 62.81 (if ΔH is greater than 0 and less than or equal to 130 J / g),

ΔT ≧ 48 ° C. (if ΔH is greater than 130 J / g);

The crisp peak is determined using at least 5% of the cumulative polymer, and if less than 5% of the polymer has an identifiable crisp peak, the crisp temperature is 30 ° C.). Microporous film comprising a polymer.

40. The method according to any one of embodiments 2 or previous embodiments, wherein the compressive-molded film of ethylene / a-olepin interpolymer is 300% strain and elastic recovery rate Re (%) in one cycle, and density d (g / cm ³ ) wherein the values of Re and d satisfy the following relationship when the ethylene / α-olefin interpolymers do not substantially comprise a crosslinked phase:

A microporous film comprising an ethylene / α-olefin interpolymer characterized by Re> 1481-1629 (d).

41. A microporous film according to any one of embodiments 2 or previous embodiments wherein the numerical values of Re and d comprise an ethylene / a-olefin interpolymer in which the following relationship:

Re> 1491-1629 (d).

42. A microporous film according to any one of embodiments 2 or previous embodiments wherein the numerical values of Re and d comprise an ethylene / a-olefin interpolymer in which the following relationship:

Re> 1501-1629 (d).

43. The microporous film of any one of embodiments 2 or previous embodiments wherein the numerical values of Re and d comprise an ethylene / a-olefin interpolymer in which the following relationship:

Re> 1511-1629 (d).

44. The molecular fraction according to any one of embodiments 2 or previous embodiments, eluting at 40 ° C. to 130 ° C. when fractionated using TREF, wherein the fraction is of a comparative random ethylene interpolymer fraction that elutes between the same temperatures Characterized by having at least 5% higher comonomer molar content, the comparative random ethylene interpolymer having the same comonomer (s) and a melt index, density within 10% of that of the ethylene / α-olefin interpolymer And an ethylene / a-olefin interpolymer having a comonomer molar content (based on total polymer).

45. The storage modulus G '(25 ° C.) at 25 ° C., and the storage modulus G' (100 ° C.) at 100 ° C., wherein G ′ (25 ° C.) versus A microporous film comprising an ethylene / α-olefin interpolymer having a ratio of G ′ (100 ° C.) in a range from about 1: 1 to about 9: 1.

46. Ethylene, which is an elastomeric polymer according to any one of embodiments 2 or previous embodiments having an ethylene content of 5 to 95 mol%, a diene content of 5 to 95 mol% and an α-olefin content of 5 to 95 mol% Microporous film comprising a / α-olefin interpolymer.

47. The microporous film of any one of the preceding embodiments, wherein the first polymer or the second polymer comprises an olefin homopolymer.

48. The microporous film of embodiment 47, wherein the olefin homopolymer is polypropylene.

49. The polypropylene of embodiment 48, wherein the polypropylene is low density polypropylene (LDPP), high density polypropylene (HDPP), high melt strength polypropylene (HMS-PP), high impact polypropylene (HIPP), isotactic polypropylene ( iPP), syndiotactic polypropylene (sPP) or a combination thereof.

50. The microporous film of embodiment 49, wherein the polypropylene is isotactic polypropylene.

51. The microporous film of any of embodiments 1-47, wherein the first polymer comprises a high density ethylene copolymer or a homopolymer and the second polymer comprises a low density ethylene copolymer.

52. The microporous film of embodiment 51, wherein the first polymer comprises high density polyethylene (HDPE) and the second polymer comprises low density polyethylene (LDPE) or linear low density polyethylene (LLDPE).

53. The microporous film of any of embodiments 1-47, wherein the first polyolefin comprises high density polyethylene (HDPE) and the second polyolefin comprises an ethylene copolymer having a composition distribution width index CDBI of greater than 50% .

54. The microporous film of any of embodiments 1-47, wherein the first polyolefin comprises high density polyethylene (HDPE) and the second polyolefin comprises an ethylene copolymer having a composition distribution width index CDBI of greater than 70% .

55. The microporous film of any of embodiments 1-47, wherein the first polyolefin comprises high density polyethylene (HDPE) and the second polyolefin comprises an ethylene copolymer having a composition distribution width index CDBI of greater than 90% .

56. The microporous film of any one of the preceding embodiments, wherein the olefin copolymer is an ethylene / propylene copolymer (EPM).

57. The microporous film of any one of the preceding embodiments, wherein the olefin homopolymer is a high density polyethylene (HDPE).

57. The microporous film of any one of the preceding embodiments, wherein the olefin terpolymer is derived from ethylene, at least 3 monoenes or dienes.

58. The microporous film of any one of the preceding embodiments, wherein the second polyolefin is a vulcanizable rubber.

59. The method of any one of embodiments 2 to 58, having a first non-coextruded portion and a second non-coextruded portion, wherein the first portion is directly bonded to the second portion, and The bond has a strength of greater than 5 g / inch, the first portion and the second portion being made of the same material and oriented substantially in the same direction); Having a thickness of less than 1.5 mils, a Gurley value of less than 50 seconds / 10 cc and a puncture strength of greater than 400 g / mil;

(i) a first polymer;

(ii) a second polymer; And

(iii) an effective amount of a polymer compatibilizer

Including a polymer blend comprising;

Wherein (iii) comprises an ethylene / α-olefin interpolymer,

Microporous films wherein the first polymer, the second polymer and the ethylene / α-olefin interpolymers are different and the ethylene / α-olefin interpolymers have one or more of the following features:

(a) Mw / Mn of about 1.7 to about 3.5, at least one melting point T _m (° C.), and density d (g / cm ³ ), where the values of T _m and d correspond to the following relationship:

T _m > -2002.9 + 4538.5 (d) -2422.2 (d) ² ); or

(b) a delta value ΔT (° C.), where ΔT, defined as the Mw / Mn of about 1.7 to about 3.5, and the heat of fusion ΔH (J / g), and the temperature difference between the highest DSC peak and the highest CRYSTAF peak The values of and ΔH have the following relationship:

ΔT> -0.1299 (ΔH) + 62.81 (if ΔH is greater than 0 and less than or equal to 130 J / g),

ΔT ≧ 48 ° C. (if ΔH is greater than 130 J / g);

The crisp peak is determined using at least 5% of the cumulative polymer, and if less than 5% of the polymer has an identifiable crisp peak, the crisp temperature is 30 ° C.); or

(c) 300% strain and elastic recovery rate Re (%) at 1 cycle, and density d (g / cm ³ ) measured with a compression-molded film of ethylene / α-olefin interpolymers, wherein the values of Re and d Satisfies the following relationship when the ethylene / α-olefin interpolymer is substantially free of the crosslinked phase:

Re> 1481-1629 (d)); or

(d) molecular fractions eluted at 40 ° C. to 130 ° C. when fractionated using TREF (the fractions having at least 5% higher comonomer molar content than that of the comparative random ethylene interpolymer fractions eluting between the same temperatures) Wherein the comparative random ethylene interpolymer has the same comonomer (s) and has a melt index, density and comonomer molar content (based on total polymer) within 10% of that of the ethylene / α-olefin interpolymers ); or

(e) storage modulus G '(25 ° C.) at 25 ° C., and storage modulus G' (100 ° C.) at 100 ° C., where the ratio of G ′ (25 ° C.) to G ′ (100 ° C.) is about 1: In the range from 1 to about 9: 1); or

(f) at least one molecular fraction characterized by having a block index of at least 0.5 to about 1 and a molecular weight distribution Mw / Mn of greater than about 1.3 and eluting at 40 ° C. to 130 ° C. when fractionated using TREF; or

(g) an average block index greater than 0 and up to about 1.0 and a molecular weight distribution Mw / Mn greater than about 1.3; or

(h) Mw / Mn from about 1.7 to about 3.5, at least one melting point T _m (° C.), and density d (g / cm ³ ), where the values of T _m and d correspond to the following relationship:

T _m > -6553.3 + 13735 (d) -7051.7 (d) ² ).

60. The high density polyethylene copolymer according to any one of embodiments 1 to 59, having a melt index (MI) of 0.1 to 100 and an alpha-olefin unit content of at least 3 carbon atoms of 0.1 to 1 mol%; And a blend comprising high density polyethylene having a viscosity average molecular weight (Mv) of at least 500000 to 5000000, wherein the blend has an Mv of 300000 to 4000000 and an alpha-olefin unit content of at least 3 carbon atoms of 0.01 to 1 mol%; And a compatibilizer, wherein the compatibilizer comprises an ethylene / a-olefin interpolymer having one or more of the following features:

(a) Mw / Mn of about 1.7 to about 3.5, at least one melting point T _m (° C.), and density d (g / cm ³ ), where the values of T _m and d correspond to the following relationship:

T _m > -2002.9 + 4538.5 (d) -2422.2 (d) ² ); or

(b) a delta value ΔT (° C.), where ΔT, defined as the Mw / Mn of about 1.7 to about 3.5, and the heat of fusion ΔH (J / g), and the temperature difference between the highest DSC peak and the highest CRYSTAF peak The values of and ΔH have the following relationship:

ΔT> -0.1299 (ΔH) + 62.81 (if ΔH is greater than 0 and less than or equal to 130 J / g),

ΔT ≧ 48 ° C. (if ΔH is greater than 130 J / g);

The crisp peak is determined using at least 5% of the cumulative polymer, and if less than 5% of the polymer has an identifiable crisp peak, the crisp temperature is 30 ° C.); or

(c) 300% strain and elastic recovery rate Re (%) at 1 cycle, and density d (g / cm ³ ) measured with a compression-molded film of ethylene / α-olefin interpolymers, wherein the values of Re and d Satisfies the following relationship when the ethylene / α-olefin interpolymer is substantially free of the crosslinked phase:

Re> 1481-1629 (d)); or

(d) molecular fractions eluted at 40 ° C. to 130 ° C. when fractionated using TREF (the fractions having at least 5% higher comonomer molar content than that of the comparative random ethylene interpolymer fractions eluting between the same temperatures) Wherein the comparative random ethylene interpolymer has the same comonomer (s) and has a melt index, density and comonomer molar content (based on total polymer) within 10% of that of the ethylene / α-olefin interpolymers ); or

(e) storage modulus G '(25 ° C.) at 25 ° C., and storage modulus G' (100 ° C.) at 100 ° C., where the ratio of G ′ (25 ° C.) to G ′ (100 ° C.) is about 1: In the range from 1 to about 9: 1); or

(f) at least one molecular fraction characterized by having a block index of at least 0.5 to about 1 and a molecular weight distribution Mw / Mn of greater than about 1.3 and eluting at 40 ° C. to 130 ° C. when fractionated using TREF; or

(g) an average block index greater than 0 and up to about 1.0 and a molecular weight distribution Mw / Mn greater than about 1.3; or

(h) Mw / Mn from about 1.7 to about 3.5, at least one melting point T _m (° C.), and density d (g / cm ³ ), where the values of T _m and d correspond to the following relationship:

T _m > -6553.3 + 13735 (d) -7051.7 (d) ² ).

61. A battery separator comprising the film of any one of the previous embodiments.

62. The battery separator of embodiment 61 comprising a lithium ion battery.

63. A membrane having a first surface, a second surface, and a plurality of micropores extending from the first surface to the second surface; And a coating covering the membrane but not filling the plurality of micropores, the gel-forming polymer and the plasticizer in a weight ratio of 1: 0.5 to 1: 3 and having a surface density of 0.4 to 0.9 mg / cm,

The membrane comprises (i) a first polymer;

(ii) a second polymer; And

(iii) an effective amount of a polymer compatibilizer

Including a polymer blend comprising,

(iii) comprises an ethylene / α-olefin interpolymer,

A separator for a lithium polymer battery, wherein the first polymer, the second polymer and the ethylene / α-olefin interpolymers are different and the ethylene / α-olefin interpolymer has one or more of the following features:

(a) Mw / Mn of about 1.7 to about 3.5, at least one melting point T _m (° C.), and density d (g / cm ³ ), where the values of T _m and d correspond to the following relationship:

T _m > -2002.9 + 4538.5 (d) -2422.2 (d) ² ); or

(b) a delta value ΔT (° C.), where ΔT, defined as the Mw / Mn of about 1.7 to about 3.5, and the heat of fusion ΔH (J / g), and the temperature difference between the highest DSC peak and the highest CRYSTAF peak The values of and ΔH have the following relationship:

ΔT> -0.1299 (ΔH) + 62.81 (if ΔH is greater than 0 and less than or equal to 130 J / g),

ΔT ≧ 48 ° C. (if ΔH is greater than 130 J / g);

The crisp peak is determined using at least 5% of the cumulative polymer, and if less than 5% of the polymer has an identifiable crisp peak, the crisp temperature is 30 ° C.); or

(c) 300% strain and elastic recovery rate Re (%) at 1 cycle, and density d (g / cm ³ ) measured with a compression-molded film of ethylene / α-olefin interpolymers, wherein the values of Re and d Satisfies the following relationship when the ethylene / α-olefin interpolymer is substantially free of the crosslinked phase:

Re> 1481-1629 (d)); or

(d) molecular fractions eluted at 40 ° C. to 130 ° C. when fractionated using TREF (the fractions having at least 5% higher comonomer molar content than that of the comparative random ethylene interpolymer fractions eluting between the same temperatures) Wherein the comparative random ethylene interpolymer has the same comonomer (s) and has a melt index, density and comonomer molar content (based on total polymer) within 10% of that of the ethylene / α-olefin interpolymer. Having); or

(e) storage modulus G '(25 ° C.) at 25 ° C., and storage modulus G' (100 ° C.) at 100 ° C., where the ratio of G ′ (25 ° C.) to G ′ (100 ° C.) is about 1: In the range from 1 to about 9: 1); or

(f) at least one molecular fraction characterized by having a block index of at least 0.5 to about 1 and a molecular weight distribution Mw / Mn of greater than about 1.3 and eluting at 40 ° C. to 130 ° C. when fractionated using TREF; or

(g) an average block index greater than 0 and up to about 1.0 and a molecular weight distribution Mw / Mn greater than about 1.3; or

(h) Mw / Mn from about 1.7 to about 3.5, at least one melting point T _m (° C.), and density d (g / cm ³ ), where the values of T _m and d correspond to the following relationship:

T _m > -6553.3 + 13735 (d) -7051.7 (d) ² ).

64. A microporous polyolefin membrane prepared from a blend of medium molecular weight high density polyethylene polymer and polyethylene wax, having a shutdown temperature of less than about 130 ° C., a porosity in the range of 30-80%, and an average pore size in the range of 0.02 to 2.0 microns. Wherein the wax comprises at least 20% by weight of the blend and at most 50% by weight of the blend, wherein the blend further comprises an ethylene / α-olefin interpolymer having one or more of the following features: Separator:

(a) Mw / Mn of about 1.7 to about 3.5, at least one melting point T _m (° C.), and density d (g / cm ³ ), where the values of T _m and d correspond to the following relationship:

T _m > -2002.9 + 4538.5 (d) -2422.2 (d) ² ); or

(b) a delta value ΔT (° C.), where ΔT, defined as the Mw / Mn of about 1.7 to about 3.5, and the heat of fusion ΔH (J / g), and the temperature difference between the highest DSC peak and the highest CRYSTAF peak The values of and ΔH have the following relationship:

ΔT> -0.1299 (ΔH) + 62.81 (if ΔH is greater than 0 and less than or equal to 130 J / g),

ΔT ≧ 48 ° C. (if ΔH is greater than 130 J / g);

The crisp peak is determined using at least 5% of the cumulative polymer, and if less than 5% of the polymer has an identifiable crisp peak, the crisp temperature is 30 ° C.); or

(c) 300% strain and elastic recovery rate Re (%) at 1 cycle, and density d (g / cm ³ ) measured with a compression-molded film of ethylene / α-olefin interpolymers, wherein the values of Re and d Satisfies the following relationship when the ethylene / α-olefin interpolymer is substantially free of the crosslinked phase:

Re> 1481-1629 (d)); or

(d) molecular fractions eluted at 40 ° C. to 130 ° C. when fractionated using TREF (the fractions having at least 5% higher comonomer molar content than that of the comparative random ethylene interpolymer fractions eluting between the same temperatures) Wherein the comparative random ethylene interpolymer has the same comonomer (s) and has a melt index, density and comonomer molar content (based on total polymer) within 10% of that of the ethylene / α-olefin interpolymers ); or

(e) storage modulus G '(25 ° C.) at 25 ° C., and storage modulus G' (100 ° C.) at 100 ° C., where the ratio of G ′ (25 ° C.) to G ′ (100 ° C.) is about 1: In the range from 1 to about 9: 1); or

(f) at least one molecular fraction characterized by having a block index of at least 0.5 to about 1 and a molecular weight distribution Mw / Mn of greater than about 1.3 and eluting at 40 ° C. to 130 ° C. when fractionated using TREF; or

(g) an average block index greater than 0 and up to about 1.0 and a molecular weight distribution Mw / Mn greater than about 1.3; or

(h) Mw / Mn from about 1.7 to about 3.5, at least one melting point T _m (° C.), and density d (g / cm ³ ), where the values of T _m and d correspond to the following relationship:

T _m > -6553.3 + 13735 (d) -7051.7 (d) ² ).

65. at least one ceramic composite layer comprising a mixture of inorganic particles in a matrix material and configured to at least block dendritic growth and prevent electronic shorts; And

One or more polyolephine microporous layers configured to block ionic flow between the anode and the cathode

Wherein the polyolefin microporous layer is

(i) a first polymer;

(ii) a second polymer; And

(iii) an effective amount of polymer compatibilizer comprising an ethylene / α-olefin interpolymer

Including a blend comprising,

The first polymer, the second polymer and the ethylene / α-olefin interpolymer are different, the ethylene / α-olefin interpolymer has one or more of the following features, and the film has any of the features described in any of the previous embodiments. Separators for high energy secondary lithium batteries with one:

(a) Mw / Mn of about 1.7 to about 3.5, at least one melting point T _m (° C.), and density d (g / cm ³ ), where the values of T _m and d correspond to the following relationship:

T _m > -2002.9 + 4538.5 (d) -2422.2 (d) ² ); or

(b) a delta value ΔT (° C.), where ΔT, defined as the Mw / Mn of about 1.7 to about 3.5, and the heat of fusion ΔH (J / g), and the temperature difference between the highest DSC peak and the highest CRYSTAF peak The values of and ΔH have the following relationship:

ΔT> -0.1299 (ΔH) + 62.81 (if ΔH is greater than 0 and less than or equal to 130 J / g),

ΔT ≧ 48 ° C. (if ΔH is greater than 130 J / g);

The crisp peak is determined using at least 5% of the cumulative polymer, and if less than 5% of the polymer has an identifiable crisp peak, the crisp temperature is 30 ° C.); or

(c) 300% strain and elastic recovery rate Re (%) at 1 cycle, and density d (g / cm ³ ) measured with a compression-molded film of ethylene / α-olefin interpolymers, wherein the values of Re and d Satisfies the following relationship when the ethylene / α-olefin interpolymer is substantially free of the crosslinked phase:

Re> 1481-1629 (d)); or

(d) molecular fractions eluted at 40 ° C. to 130 ° C. when fractionated using TREF (the fractions having at least 5% higher comonomer molar content than that of the comparative random ethylene interpolymer fractions eluting between the same temperatures) Wherein the comparative random ethylene interpolymer has the same comonomer (s) and has a melt index, density and comonomer molar content (based on total polymer) within 10% of that of the ethylene / α-olefin interpolymers ); or

(e) storage modulus G '(25 ° C.) at 25 ° C., and storage modulus G' (100 ° C.) at 100 ° C., where the ratio of G ′ (25 ° C.) to G ′ (100 ° C.) is about 1: In the range from 1 to about 9: 1); or

(f) at least one molecular fraction characterized by having a block index of at least 0.5 to about 1 and a molecular weight distribution Mw / Mn of greater than about 1.3 and eluting at 40 ° C. to 130 ° C. when fractionated using TREF; or

(g) an average block index greater than 0 and up to about 1.0 and a molecular weight distribution Mw / Mn greater than about 1.3; or

(h) Mw / Mn from about 1.7 to about 3.5, at least one melting point T _m (° C.), and density d (g / cm ³ ), where the values of T _m and d correspond to the following relationship:

T _m > -6553.3 + 13735 (d) -7051.7 (d) ² ).

66. Polyolefin microporous membrane comprising the microporous film of any of the previous embodiments and having a coating

Battery separator comprising a.

67. The battery separator of embodiment 66, wherein the coating contains a surfactant and an ethylene vinyl alcohol copolymer.

68. A first and third microporous strength layer interposed with a shutdown layer, wherein the shutdown layer is a microporous membrane prepared by a phase inversion process, wherein the strength layer is prepared by an stretching method, and At least one of the layers comprises the microporous film of any one of the previous embodiments.

69. An article comprising the microporous film or membrane of any one of the previous embodiments.

70. The article of embodiment 69, wherein the article is selected from the group consisting of coated membranes, multilayer structures, batteries, filter media, and proton exchange membranes.

71. The article of embodiment 70 selected from the group consisting of alkaline batteries, lithium ion primary batteries, lead acid batteries and fuel cell batteries.

72. (i) a first polymer;

(ii) a second polymer; And

(iii) an effective amount of a polymer compatibilizer

Blending a starting material comprising a filler or oil; And

Removing filler or oil during the film making process to create porosity in the film

Including,

(iii) comprises an ethylene / α-olefin interpolymer,

The microporous film having different characteristics of the first polymer, the second polymer and the ethylene / α-olefin interpolymer, wherein the ethylene / α-olefin interpolymer has one or more of the following characteristics, and has the characteristics of any of the previous embodiments, or Manufacturing Method Of Membrane:

(a) Mw / Mn of about 1.7 to about 3.5, at least one melting point T _m (° C.), and density d (g / cm ³ ), where the values of T _m and d correspond to the following relationship:

T _m > -2002.9 + 4538.5 (d) -2422.2 (d) ² ); or

(b) a delta value ΔT (° C.), where ΔT, defined as the Mw / Mn of about 1.7 to about 3.5, and the heat of fusion ΔH (J / g), and the temperature difference between the highest DSC peak and the highest CRYSTAF peak The values of and ΔH have the following relationship:

ΔT> -0.1299 (ΔH) + 62.81 (if ΔH is greater than 0 and less than or equal to 130 J / g),

ΔT ≧ 48 ° C. (if ΔH is greater than 130 J / g);

The crisp peak is determined using at least 5% of the cumulative polymer, and if less than 5% of the polymer has an identifiable crisp peak, the crisp temperature is 30 ° C.); or

(c) 300% strain and elastic recovery rate Re (%) at 1 cycle, and density d (g / cm ³ ) measured with a compression-molded film of ethylene / α-olefin interpolymers, wherein the values of Re and d Satisfies the following relationship when the ethylene / α-olefin interpolymer is substantially free of the crosslinked phase:

Re> 1481-1629 (d)); or

(d) molecular fractions eluted at 40 ° C. to 130 ° C. when fractionated using TREF (the fractions having at least 5% higher comonomer molar content than that of the comparative random ethylene interpolymer fractions eluting between the same temperatures) Wherein the comparative random ethylene interpolymer has the same comonomer (s) and has a melt index, density and comonomer molar content (based on total polymer) within 10% of that of the ethylene / α-olefin interpolymers ); or

(e) storage modulus G '(25 ° C.) at 25 ° C., and storage modulus G' (100 ° C.) at 100 ° C., where the ratio of G ′ (25 ° C.) to G ′ (100 ° C.) is about 1: In the range from 1 to about 9: 1); or

(f) at least one molecular fraction characterized by having a block index of at least 0.5 to about 1 and a molecular weight distribution Mw / Mn of greater than about 1.3 and eluting at 40 ° C. to 130 ° C. when fractionated using TREF; or

(g) an average block index greater than 0 and up to about 1.0 and a molecular weight distribution Mw / Mn greater than about 1.3; or

(h) Mw / Mn from about 1.7 to about 3.5, at least one melting point T _m (° C.), and density d (g / cm ³ ), where the values of T _m and d correspond to the following relationship:

T _m > -6553.3 + 13735 (d) -7051.7 (d) ² ).

73. The method of embodiment 72, further comprising functionalizing the film.

74. The method of embodiment 72 or 73, wherein the starting material has a polymer content of less than about 50 weight percent.

75. The method of any one of embodiments 72 to 74, wherein the starting material comprises more than 60% oil.

76. The method of any one of embodiments 72 to 75, wherein the starting material comprises more than 95% oil.

77. The method of any one of embodiments 72 to 76, wherein the starting material comprises a wax.

78. providing a nonwoven flat sheet; Providing a microporous membrane; Providing an adhesive solution comprising a solvent, a swellable polymer and a humectant; Coating the sheet, or the film, or both the sheet and the film with an adhesive solution; Laminating the nonwoven flat sheet and the film; And forming a separator, wherein the film comprises the film of any one of embodiments 1-72.

79. A battery separator containing at least 80% by weight of a polymer selected from the group consisting of polypropylene, polyethylene and copolymers thereof, having a transverse tear resistance of at least about 50 kgf / cm ² , a single layer or coextruded multilayer membrane. A process for preparing a microporous membrane suitable for use as the above, wherein the microporous membrane comprises the film of any one of embodiments 1 to 72,

Extruding the film precursor by the blown film method at a blow-up ratio of at least 1.5;

Annealing the film precursor; And

Stretching the resulting annealed film precursor to form a microporous membrane.

Test Methods

In the following examples, the following analytical techniques were used:

GPC Method for Samples 1-4 and A-C

Using an automated liquid-handling robot equipped with a heated needle set at 160 ° C., sufficient 1,2,4-trichlorobenzene stabilized by 300 ppm Ionol was added to each dried polymer sample. A final concentration of 30 mg / mL was obtained. A small glass stir bar was placed in each tube and the sample was heated to 160 ° C. for 2 hours in a heated orbital shaker rotating at 250 rpm. The polymer concentrate was then diluted to 1 mg / ml using an automated liquid-handling robot and a heated needle set at 160 ° C.

Molecular weight data for each sample was measured using the Simix Rapid GPC system. Three Plgels placed in series and heated to 160 ° C. in a Helium-purged 1,2-dichlorobenzene stabilized with 300 ppm ionol using a Gilson 350 pump set at a flow rate of 2.0 ml / min. Pumped as a mobile phase through a 10 micrometer (μm) mixed B 300 mm × 7.5 mm column. A Polymer Labs ELS 1000 detector was used with an evaporator set at 250 ° C., a nebulizer set at 165 ° C., and a nitrogen flow rate set at 1.8 SLM at a N ₂ pressure of 60-80 psi (400-600 kPa). The polymer samples were heated to 160 ° C. and each sample was injected into a 250 μl loop using the liquid-handling robot and the heated needle. A series of analyzes of the polymer samples using two switched loops and overlapping injections was used. Sample data was collected and analyzed using Symyx Epoch (tradename) software. Peaks were manually integrated and molecular weight information was recorded without correction against the polystyrene standard calibration curve.

Standard CRYSTAF Method

Branch distribution was measured by crystallization analysis fractionation (CRYSTAF) using a Kristaf 200 device commercially available from PolymerChar, Valencia, Spain. Samples were dissolved in 1,2,4-trichlorobenzene at 160 ° C. for 1 hour (0.66 mg / mL) and stabilized at 95 ° C. for 45 minutes. Sampling temperature ranged from 95 ° C to 30 ° C with a cooling rate of 0.2 ° C / min. The polymer solution concentration was measured using an infrared detector. The cumulative soluble concentration was measured as the polymer crystallized while lowering the temperature. The analytical derivative of the cumulative profile reflected the short chain branch distribution of the polymer.

The Kristaf peak temperature and area were confirmed by the peak analysis module included in the Kristaf software (version 2001.b, Polymer Char, Valencia, Spain). The CRYSTAF peak search routine identified the peak temperature to the maximum in the dW / dT curve and the area between the largest amount of bends on either side of the peak identified in the differential curve. To calculate the CRYSTAF curve, preferred processing parameters used smoothing parameters of a temperature limit of 70 ° C. and above a temperature limit of 0.1, and below a temperature limit of 0.3.

DSC Standard Methods (Samples 1-4 and A-C et al.)

Differential scanning calorimetry results were measured using a TAI model Q1000 DSC equipped with an RCS cooling accessory and an automatic sampler. A nitrogen purge gas flow of 50 ml / min was used. The samples were compressed into thin films and melted in a press at about 175 ° C. and then air-cooled to room temperature (25 ° C.). 3-10 mg of material was then cut into 6 mm diameter disks, accurately weighed, placed in a lightweight aluminum pan (about 50 mg) and then crimped off. The thermal behavior of the samples was investigated with the following temperature profiles. The sample was rapidly heated to 180 ° C. and kept isothermal for 3 minutes to remove any previous thermal history. The sample was then cooled to −40 ° C. at a cooling rate of 10 ° C./min and held at −40 ° C. for 3 minutes. The sample was then heated to 150 ° C. at a heating rate of 10 ° C./min. Cooling and second heating curves were recorded.

The DSC melt peak was measured as the maximum of heat flow rate (W / g) relative to the linear baseline drawn between −30 ° C. and the melting end point. The heat of fusion was measured as the area under the melting curve between −30 ° C. and the melting end point using a linear baseline.

GPC Method (Samples 1-4 and A-C et al.)

Gel permeation chromatography systems consisted of Polymer Laboratories Model PL-210 or Polymer Laboratories Model PL-220 instruments. The column and carousel compartments were operated at 140 ° C. Three Polymer Laboratories 10-micrometer Mixed-B columns were used. The solvent was 1,2,4-trichlorobenzene. Samples were prepared at a concentration of 0.1 grams of polymer in 50 milliliters of solvent containing 200 ppm of butylated hydroxytoluene (BHT). Samples were prepared by gently stirring at 160 ° C. for 2 hours. The injection volume used was 100 microliters and the flow rate was 1.0 ml / min.

Calibration of the GPC column set is performed by 21 narrow molecular weight distribution polystyrene standards with molecular weights ranging from 580 to 8,400,000, arranged in six “cocktail” mixtures with at least 10 intervals between each molecular weight. It was. Standards were purchased from Polymer Laboratories, Shropshire, UK. Polystyrene standards were prepared in 0.025 grams in 50 milliliters of solvent for molecular weights greater than 1,000,000 and 0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000. Polystyrene standards were dissolved at 80 ° C. with gentle stirring for 30 minutes. The narrow standard mixture was carried out first and then in order of decreasing maximum molecular weight component to minimize work degradation. Polystyrene standard peak molecular weights were converted to polyethylene molecular weight using the following equation (as described in Williams and Ward, J. Polym. Sci., Polym. Let ., 6, 621 (1968)): M _polyethylene = 0.431 (M _polystyrene ).

Polyethylene equivalent molecular weight was calculated using Viscotek TriSEC software version 3.0.

Compression set

Compression set was measured according to ASTM D 395. Samples were prepared by laminating round discs of diameter 25.4 mm with thicknesses of 3.2 mm, 2.0 mm and 0.25 mm until the total thickness reached 12.7 mm. The discs were cut from 12.7 cm x 12.7 cm compression molded plaques formed by hot press under the following conditions: pressureless at 190 ° C. for 3 minutes, then 86 MPa at 190 ° C. for 2 minutes, followed by cooling with running cold water inside the press. 86 MPa.

density

Samples for density measurement were prepared according to ASTM D 1928. Measurements were made within 1 hour of sample pressurization using ASTM D792, Method B.

Flexural / Secant Modulus / Storage Modulus

Samples were compression molded using ASTM D 1928. Flexural modulus and 2% secant modulus were measured according to ASTM D-790. Storage modulus was measured according to ASTM D 5026-01 or equivalent technique.

Optical properties

The 0.4 mm thick film was compression molded using a hot press (Carver model # 4095-4PR1001R). The pellet was placed between polytetrafluoroethylene sheets and heated at 190 ° C. for 3 minutes at 55 psi (380 kPa), then 3 minutes at 1.3 MPa and then 3 minutes at 2.6 MPa. The film was then cooled in a press through which cooling water flowed at 1.3 MPa for 1 minute. Compression molded films were used for optical measurements, tensile behavior, recovery and stress relaxation rates.

Transparency was measured using BYK Gardner Haze-gard as specified in ASTM D 1746.

45 ° gloss was measured using BYK Gardner Glossmeter Microgloss 45 ° as specified in ASTM D-2457.

Internal turbidity was measured based on ASTM D 1003 Procedure A using BYK Gardner Haze-Guard. Mineral oil was applied to the film surface to remove surface scratches.

Mechanical Properties-Tensile, Hysteresis and Tear

The stress-strain behavior at uniaxial tension was measured using ASTM D 1708 microtensile specimens. Samples were stretched by Instron at 500C / min at 21 ° C. Tensile strength and elongation at break were recorded from the average of five specimens.

100% and 300% hysteresis were measured from periodic loads up to 100% and 300% strain using an ASTM D 1708 microtensile specimen with an Instron ™ instrument. Samples were loaded and unloaded at 21 ° C. at 267% / min for 3 cycles. Periodic experiments at 300% and 80 ° C were performed using an environmental chamber. In the 80 ° C. experiment, the samples were equilibrated for 45 minutes at the test temperature before testing. In a 21 ° C., 300% strain periodic experiment, the shrinkage stress at 150% strain from the first unload cycle was recorded. The percent recovery in all experiments was calculated from the first unload cycle using the strain at which the load returned to the baseline. Recovery rate (%) is defined as follows.

Where ε _f is the strain taken against the cyclic load and ε _s is the strain when the load returns to the baseline during the first unloading cycle.

Stress relaxation rates were measured for 12 hours at 50% strain and 37 ° C. using an Instron ™ instrument equipped with an environmental chamber. The gauge geometry was 76 mm x 25 mm x 0.4 mm. After equilibrating at 37 ° C. for 45 minutes in an environmental chamber, the sample was stretched to 50% strain at 333% / min. The stress was recorded as a function of time for 12 hours. The stress relaxation ratio (%) after 12 hours was calculated using the following equation.

In the formula, L ₀ is the load at 50% strain at time 0, and L ₁₂ is the load at 50% strain after 12 hours.

Tensile notch tear experiments were performed on samples having a density of 0.88 g / cc or less using an Instron ™ instrument. The geometry consisted of a 76 mm x 13 mm x 0.4 mm gauge area with a 2 mm notch cut into samples at half the length of the specimen. The sample was stretched to 508 mm / min at 21 ° C. until it broke. Tear energy was calculated as the area under the stress-elongation curve, up to strain at maximum load. The average of three or more specimens was recorded.

TMA

Thermomechanical analysis (penetration temperature) was performed on a 30 mm diameter x 3.3 mm thick compression molded disk that was formed for 5 minutes at 180 ° C. and 10 MPa molding pressure and then air quenched. The instrument used was TMA 7 (brand available from Perkin-Elmer). In the test a probe with a radius of 1.5 mm (P / N N519-0416) was applied to the surface of the sample disc with a force of 1 N. The temperature was raised from 25 ° C to 5 ° C / min. Probe penetration distance was measured as a function of temperature. The experiment was terminated when the probe had penetrated 1 mm into the sample.

DMA

Thermomechanical analysis (DMA) was performed on compression molded discs formed at 180 ° C., 10 MPa pressure in a hot press for 5 minutes and then water cooled to 90 ° C./min in the press. The test was performed using an ARES controlled strain rheometer (TA instrument) equipped with a double cantilever fixture for the torsion test.

1.5 mm plaques were compressed and cut into bars measuring 32 × 12 mm. Samples were clamped at both ends between fixtures at 10 mm intervals (grip spacing (ΔL)) and subsequent temperature steps were applied from −100 ° C. to 200 ° C. (5 ° C. per step). At each temperature, the torsional modulus (G ') was measured at an angular frequency of 10 rad / s, and the strain amplitude was maintained between 0.1% and 4% to ensure that the torque was sufficient and the measurement remained in a linear system.

An initial static force of 10 g was maintained (automatic tension mode) to prevent sagging of the sample when thermal expansion occurred. As a result, the grip spacing (ΔL) increased with the temperature, especially at temperatures above the melting or softening point of the polymer sample. The test was stopped at the maximum temperature or when the spacing between the fixtures reached 65 mm.

Gully figures

Gurley numbers were measured as the time it takes for 10 cc of air to flow through a 1 inch ² membrane at a water pressure of 12.2 inches.

Melt index

Melt index or I ₂ was measured according to ASTM D 1238, Condition 190 ° C./2.16 kg. In addition, the melt index or I ₁₀ was measured according to ASTM D 1238, condition 190 ° C./10 kg.

ATREF

U.S. Patent 4,798,081 and Wilde, L .; Ryle, TR; Knobeloch, DC; Peat, IR; Determination of Branching Distributions in Polyethylene and Ethylene Copolymers , J. polym. Analytical Temperature Rise Elution Fractionation (ATREF) analysis was performed according to the method described in Sci., 20, 441-455 (1982). The composition to be analyzed was dissolved in trichlorobenzene and crystallized by slowly lowering the temperature to 20 ° C. at a cooling rate of 0.1 ° C./min in a column containing an inert support (stainless steel shot). The column was equipped with an infrared detector. The temperature of the eluting solvent (trichlorobenzene) was then slowly increased from 20 ° C. to 120 ° C. at a rate of 1.5 ° C./min, eluting the polymer sample crystallized from the column to generate an ATREF chromatogram curve.

¹³ C NMR Analysis

Samples were prepared by adding a 50/50 mixture (approximately 3 g) of tetrachloroethane-d ² / orthodichlorobenzene to 0.4 g of sample in a 10 mm NMR tube. The sample was dissolved and homogenized by heating the tube and its contents to 150 ° C. Data was collected using a JEOL Eclipse 400 MHz spectrometer or a Varian Unity Plus 400 MHz spectrometer, corresponding to a ¹³ C resonance frequency of 100.5 MHz. Data was obtained using 4000 transients per data file with a 6 second pulse repetition delay. Several data files were added together to obtain minimal signal-to-noise for quantitative analysis. At a minimum file size of 32K data points, the spectral width was 25,000 Hz. Samples were analyzed at 130 ° C. in a 10 mm wide band probe. Randall's triad method (Randall, JC; JMS-Rev. Macromol. Chem. Phys., C29, 201-317 (1989)), incorporated herein by reference in its entirety) Monomer incorporation was measured.

Polymer Fractionation by TREF

Large scale TREF fractionation was performed by dissolving 15-20 g of polymer in 2 liters of 1,2,4-trichlorobenzene (TCB) by stirring at 160 ° C. for 4 hours. The polymer solution was subjected to 15 psig (100 kPa) nitrogen, 30 to 40 mesh (600 to 425 μm) spherical industrial quality glass beads (Potters, Brownwood HC 30 Box 20, 76801, USA). Industries; and stainless steel, 0.028 "(0.7 mm) diameter cutting wire shots (available from Pellets, Inc., North Tornawanda Industrial Drive 63, 14120, NY, USA). Was applied on a 3 inch x 4 ft (7.6 cm x 12 cm) steel column filled with a 60:40 (v: v) mixture of the column in a thermally controlled oil jacket, initially set at 160 ° C. The column was first rapidly cooled to 125 ° C., then slowly cooled to 0.04 ° C./min to 20 ° C. and held for 1 hour The new TCB was brought to about 65 ml / min by increasing the temperature to 0.167 ° C./min. Introduced.

Approximately 2000 ml portions of the eluate from the preparative TREF column were collected in 16 stations of heated fraction collector. The polymer was concentrated in each fraction using a rotary evaporator until about 50-100 ml of polymer solution remained. After leaving the concentrate overnight, excess methanol was added, filtered and rinsed (approximately 300-500 ml of methanol, including the final rinse). The filtration step was performed in a 3-position vacuum assisted filtration station using a 5.0 μm polytetrafluoroethylene coated filter paper (available from Osmonics Inc., Cat # Z50WP04750). The filtered fractions were dried overnight in a vacuum oven at 60 ° C., weighed on an analytical balance and then further tested.

Melt strength

Melt strength (MS) was measured using a capillary rheometer equipped with a 2.1 mm diameter, 20: 1 die with an inlet angle of approximately 45 °. After equilibrating the sample at 190 ° C. for 10 minutes, the piston was run at a speed of 1 inch / minute (2.54 cm / minute). Standard test temperature was 190 ° C. Samples were pulled uniaxially with an acceleration of 2.4 mm / sec ² up to a set of acceleration nips located 100 mm below the die. The required tensile force was recorded as a function of the winding speed of the nip rolls. The maximum tensile force obtained during the test was defined as the melt strength. In the case of a polymer melt exhibiting pull resonance, the tensile force before the start of pull resonance was taken as the melt strength. Melt strength was reported in centinewtons (“cN”).

catalyst

When used, the term “overnight” refers to approximately 16 to 18 hours, the term “room temperature” refers to a temperature of 20 to 25 ° C., and the term “mixed alkanes” from the ExxonMobil Chemical Company under the trade name Isopar E ( Refers to a mixture of C _6-9 aliphatic hydrocarbons sold under Isopar E®. If a compound name does not match its structural representation herein, the structural representation will prevail. Synthesis of all metal complexes and preparation of all screening experiments were performed in a dry nitrogen atmosphere using dry box technology. All solvents used were HPLC grade and used after drying.

MMAO refers to modified methylalumoxane, ie triisobutylaluminum modified methylalumoxane, available from Akzo-Noble Corporation. Preparation of the catalyst (B1) was carried out as follows.

b. Preparation of (1-methylethyl) (2-hydroxy-3,5-di (t-butyl) phenyl) methylimine

3,5-di-t-butylsalicylaldehyde (3.00 g) was added to 10 mL of isopropylamine. The solution rapidly turned bright yellow. After stirring for 3 hours at ambient temperature, the volatiles were removed under vacuum to yield a light yellow crystalline solid (yield 97%).

c. Preparation of 1,2-bis- (3,5-di-t-butylphenylene) (1- (N- (1-methylethyl) imino) methyl) (2-oxoyl) zirconium dibenzyl

A solution of (1-methylethyl) (2-hydroxy-3,5-di (t-butyl) phenyl) imine (605 mg, 2.2 mmol) in 5 mL toluene was added Zr (CH ₂ Ph) ₄ in 50 mL toluene. (500 mg, 1.1 mmol) was added slowly to the solution. The resulting dark yellow solution was stirred for 30 minutes. Removal of solvent under reduced pressure gave the desired product as a reddish brown solid.

Preparation of the catalyst (B2) was carried out as follows.

d. Preparation of (1- (2-methylcyclohexyl) ethyl) (2-oxoyl-3,5-di (t-butyl) phenyl) imine

2-methylcyclohexylamine (8.44 mL, 64.0 mmol) was dissolved in methanol (90 mL) and di-t-butylsalicylaldehyde (10.00 g, 42.67 mmol) was added. The reaction mixture was stirred for 3 hours and then cooled to -25 ° C for 12 hours. The resulting yellow solid precipitate was collected by filtration, washed with cold methanol (2 × 15 mL) and then dried under reduced pressure. 11.17 g of a yellow solid were obtained. ¹ H NMR was consistent with the desired product as an isomer mixture.

e. Preparation of bis- (1- (2-methylcyclohexyl) ethyl) (2-oxoyl-3,5-di (t-butyl) phenyl) imino) zirconium dibenzyl

Zr in 600 mL toluene with a solution of (1- (2-methylcyclohexyl) ethyl) (2-oxoyl-3,5-di (t-butyl) phenyl) imine (7.63 g, 23.2 mmol) in 200 mL toluene To the solution of (CH ₂ Ph) ₄ (5.28 g, 11.6 mmol) was added slowly. The resulting dark yellow solution was stirred at 25 ° C. for 1 hour. The solution was further diluted with 680 mL toluene to give a solution of concentration 0.00783 M.

Cocatalyst 1 : Long-chain trialkylamines (Armeen® M2HT, Liquid-Nobel, Inc.), substantially as disclosed in US Pat. No. 5,919,983, Example 2. Available from)), methyldi (C _14-18 alkyl) ammonium salt of tetrakis (pentafluorophenyl) borate (hereafter aluminum borate), prepared by reacting HCl and Li [B (C ₆ F ₅ ) ₄ ] ) Mixture.

Cocatalyst 2 : Mixed C _14-18 alkyldimethylammonium salt of bis (tris (pentafluorophenyl) -aluman) -2-undecylimidazole, prepared according to US Pat. No. 6,395,671, Example 16.

Transfer agent : The transfer agent used is diethylzinc (DEZ, SA1), di (i-butyl) zinc (SA2), di (n-hexyl) zinc (SA3), triethylaluminum (TEA, SA4), trioctylaluminum ( SA5), triethylgallium (SA6), i-butylaluminum bis (dimethyl (t-butyl) siloxane) (SA7), i-butylaluminum bis (di (trimethylsilyl) amide) (SA8), n-octylaluminum di (Pyridine-2-methoxide) (SA9), bis (n-octadecyl) i-butylaluminum (SA10), i-butylaluminum bis (di (n-pentyl) amide) (SA11), n-octylaluminum bis (2,6-di-t-butylphenoxide) (SA12), n-octylaluminum di (ethyl (1-naphthyl) amide) (SA13), ethylaluminum bis (t-butyldimethylsiloxide) (SA14) , Ethylaluminum di (bis (trimethylsilyl) amide) (SA15), ethylaluminum bis (2,3,6,7-dibenzo-1-azacycloheptanamide) (SA16), n-octyl aluminum beads (2 , 3,6,7-dibenzo-1-azacycloheptanamide) (SA17), n-octylaluminum bis (dimethyl (t-part ) A siloxane-oxide (SA18), ethyl zinc (2,6-diphenyl-phenoxide) (SA19), and zinc acetate (t- butoxide) (SA20).

Examples 1-4, and Comparative Example A ^*  To C ^*

General High Throughput Parallel Polymerization Conditions

The polymerization is carried out using a high throughput parallel polymerization reactor (PPR) available from Symyx technologies, Inc., and is described in substantially US Pat. Nos. 6,248,540, 6,030,917, 6,362,309, Work was performed according to Nos. 6,306,658 and 6,316,663. Ethylene copolymerization was carried out at 130 ° C. and 200 psi (1.4 MPa) with the required ethylene using 1.2 equivalents of cocatalyst 1 (1.1 equivalents when MMAO was present) based on the total catalyst used. A series of polymerizations was carried out in a parallel pressure reactor (PPR) containing 48 individual reactor cells in a 6 × 8 arrangement with pre-weighed glass tubes fixed. The working volume in each reactor cell was 6000 μl. Each cell was stirred by a separate stirring paddle to control temperature and pressure. Monomer gas and quench gas were fed directly into the PPR apparatus into the tube and controlled by an automatic valve. Liquid reagents were robotically added to each reactor cell by syringe, and the solvent of the reservoir was mixed alkanes. The order of addition was mixed alkane solvent (4 ml), ethylene, 1-octene comonomer (1 ml), cocatalyst 1 or cocatalyst 1 / MMAO mixture, transfer agent, and catalyst or catalyst mixture. When using a mixture of cocatalyst 1 and MMAO or a mixture of two catalysts, the premix was premixed in small vials just prior to addition of the reagents to the reactor. If one reagent was omitted in the experiment, the order of addition was otherwise maintained. The polymerization was carried out for approximately 1 to 2 minutes until the desired ethylene consumption was reached. After quenching with CO, the reactor was cooled and the glass tube was unloaded. The tubes were transferred to a centrifuge / vacuum drying apparatus and dried at 60 ° C. for 12 hours. The tube containing the dried polymer was weighed and the net yield of the polymer was obtained from the difference between its weight and the container weight. The results are shown in Table 1. In Table 1 and elsewhere herein, the comparative compound is indicated by an asterisk ( ^* ).

Examples 1-4 show a very narrow MWD, essentially monomodal copolymer, and a broad molecular weight distribution product of bimodal in the absence of DEZ (mixture of separately prepared polymers) when DEZ is present As evidenced by the formation of, the synthesis of linear block copolymers according to the invention is shown. Due to the fact that catalyst (A1) is known to incorporate more octene compared to catalyst (B1), different blocks or segments of the resulting copolymers of the invention are distinguishable on the basis of branching or density.

TABLE 1

Polymers prepared according to the present invention have a relatively narrow polydispersity (Mw / Mn) and greater block copolymer content (terpolymers, quaternary copolymers, or more) compared to polymers prepared in the absence of transfer agents. Able to know.

Additional characterization data for the polymers in Table 1 were determined with reference to the figures. More specifically, the DSC and ATREF results are shown below.

The DSC curve for the polymer of Example 1 showed a melting point (T _m ) of 115.7 ° C. with a heat of fusion of 158.1 J / g. The corresponding CRYSTAF curve shows the tallest peak at 34.5 ° C. and a peak area of 52.9%. The difference between the DSC T _m and the T _crisp was 81.2 ° C.

The DSC curve for the polymer of Example 2 showed a peak with a melting point (T _m ) of 109.7 ° C. with a heat of fusion of 214.0 J / g. The corresponding CRYSTAF curve shows the tallest peak at 46.2 ° C. and a peak area of 57.0%. The difference between the DSC T _m and the T _crisp was 63.5 ° C.

The DSC curve for the polymer of Example 3 showed a peak with a melting point (T _m ) of 120.7 ° C. with a heat of fusion of 160.1 J / g. The corresponding CRYSTAF curve shows the tallest peak at 66.1 ° C. and a peak area of 71.8%. The difference between the DSC T _m and the T _crisp was 54.6 ° C.

The DSC curve for the polymer of Example 4 showed a peak with a melting point (T _m ) of 104.5 ° C. with a heat of fusion of 170.7 J / g. The corresponding CRYSTAF curve shows the highest peak at 30 ° C. and a peak area of 18.2%. The difference between the DSC T _m and the T _crisp was 74.5 ° C.

The DSC curve for Comparative Example A ^* showed a melting point (T _m ) of 90.0 ° C with a heat of fusion of 86.7 J / g. The corresponding CRYSTAF curve shows the tallest peak at 48.5 ° C. and a peak area of 29.4%. Both of these values were consistent with low density resins. The difference between the DSC T _m and the T _crisp was 41.8 ° C.

The DSC curve for Comparative Example B ^* showed a melting point (T _m ) of 129.8 ° C. with a heat of fusion of 237.0 J / g. The corresponding CRYSTAF curve shows the tallest peak at 82.4 ° C. and a peak area of 83.7%. Both of these values were consistent with high density resins. The difference between the DSC T _m and the T _crisp was 47.4 ° C.

The DSC curve for Comparative Example C ^* showed a melting point (T _m ) of 125.3 ° C. with a heat of fusion of 143.0 J / g. The corresponding CRYSTAF curve shows the highest peak at 81.8 ° C. and the peak area of 34.7% as well as the lower crystalline peak at 52.4 ° C. The spacing between the two peaks was consistent with the presence of high and low crystalline polymers. The difference between the DSC T _m and the T _crisp was 43.5 ° C.

Examples 5 to 19, Comparative Example D ^*  To F ^* , Continuous solution polymerization, catalyst A1 / B2 + DEZ

Continuous solution polymerization was carried out in a computer controlled autoclave reactor equipped with an internal stirrer. Purified mixed alkane solvent (Isopar ™ E) available from ExxonMobil Chemical Company, 2.70 lbs / hr (1.22 kg / hr) of ethylene, 1-octene and hydrogen (if used) were internal thermocouple and temperature It was fed to a 3.8 L reactor equipped with a control jacket. The solvent fed to the reactor was measured by mass-flow controller. A variable speed diaphragm pump was used to control the solvent flow rate and pressure into the reactor. At the pump outlet, the side stream was taken to provide flush flow for the catalyst and cocatalyst 1 injection line and reactor stirrer. These flows were measured by a Micro-Motion mass flow meter and controlled by a control valve or by manual adjustment of the needle valve. The remaining solvent was combined with 1-octene, ethylene and hydrogen (if used) and fed to the reactor. A mass flow controller was used to feed hydrogen to the reactor if necessary. The temperature of the solvent / monomer solution was adjusted using a heat exchanger and then introduced into the reactor. The stream was introduced at the bottom of the reactor. The catalyst component solution was metered in using a pump and a mass flow meter, combined with the catalyst flush solvent and introduced to the bottom of the reactor. The reactor was run in liquid-filled state at 500 psig (3.45 MPa) with vigorous stirring. The product was withdrawn through the outlet line at the top of the reactor. All outlet lines of the reactor were vapor traced and insulated. A small amount of water was added into the outlet line with any stabilizer or other additives and the polymerization was stopped by passing the mixture through a static mixer. The product stream was then heated through a heat exchanger and then devolatilized. The polymer product was recovered by extrusion using a devolatilization extruder and a water cooled pelletizer. Process details and results are listed in Table 2. Selected polymer properties are listed in Table 3.

TABLE 2

^* Comparative Example (not an embodiment of the present invention)

¹ standard cm ³ / min

² [N- (2,6-di (1-methylethyl) phenyl) amido) (2-isopropylphenyl) (α-naphthalen-2-diyl (6-pyridin-2-diyl) methane)] hafnium dimethyl

³ bis- (1- (2-methylcyclohexyl) ethyl) (2-oxoyl-3,5-di (t-butyl) phenyl) imino) zirconium dibenzyl

⁴ molar ratio in reactor

⁵ Polymer Producing Rate

⁶ % conversion of ethylene in the reactor

⁷ Efficiency, kg polymer / g M (where g M = g Hf + g Zr)

TABLE 3

The resulting polymer was tested by DSC and ATREF as in the above examples. The results were as follows.

The DSC curve for the polymer of Example 5 showed a peak with a melting point (T _m ) of 119.6 ° C. with a heat of fusion of 60.0 J / g. The corresponding CRYSTAF curve shows the tallest peak at 47.6 ° C. and a peak area of 59.5%. DSC delta T between T _m and _{Chris tarp} was 72.0 ℃.

The DSC curve for the polymer of Example 6 showed a peak with a melting point (T _m ) of 115.2 ° C. with a heat of fusion of 60.4 J / g. The corresponding CRYSTAF curve shows the tallest peak at 44.2 ° C. and a peak area of 62.7%. DSC delta T between T _m and _{Chris tarp} was 71.0 ℃.

The DSC curve for the polymer of Example 7 showed a peak with a melting point of 121.3 ° C. with a heat of fusion of 69.1 J / g. The corresponding CRYSTAF curve shows the tallest peak at 49.2 ° C. and a peak area of 29.4%. DSC delta T between T _m and _{Chris tarp} was 72.1 ℃.

The DSC curve for the polymer of Example 8 showed a peak with a melting point (T _m ) of 123.5 ° C. with a heat of fusion of 67.9 J / g. The corresponding CRYSTAF curve shows the tallest peak at 80.1 ° C. and a peak area of 12.7%. The delta between the DSC T _m and the T _crisp was 43.4 ° C.

The DSC curve for the polymer of Example 9 showed a peak with a melting point (T _m ) of 124.6 ° C. with a heat of fusion of 73.5 J / g. The corresponding CRYSTAF curve shows the tallest peak at 80.8 ° C. and a peak area of 16.0%. DSC delta T between T _m and _{Chris tarp} was 43.8 ℃.

The DSC curve for the polymer of Example 10 showed a peak with a melting point (T _m ) of 115.6 ° C. with a heat of fusion of 60.7 J / g. The corresponding CRYSTAF curve shows the highest peak at 40.9 ° C. and a peak area of 52.4%. DSC delta T between T _m and _{Chris tarp} was 74.7 ℃.

The DSC curve for the polymer of Example 11 showed a peak with a melting point (T _m ) of 113.6 ° C. with a heat of fusion of 70.4 J / g. The corresponding CRYSTAF curve shows the tallest peak at 39.6 ° C. and a peak area of 25.2%. DSC delta T between T _m and _{Chris tarp} was 74.1 ℃.

The DSC curve for the polymer of Example 12 showed a peak with a melting point (T _m ) of 113.2 ° C. with a heat of fusion of 48.9 J / g. The corresponding CRYSTAF curve did not show a peak above 30 ° C. (thus setting the T _CRYSTAF to 30 ° C. for further calculation). DSC delta T between T _m and _{Chris tarp} was 83.2 ℃.

The DSC curve for the polymer of Example 13 showed a peak with a melting point (T _m ) of 114.4 ° C. with a heat of fusion of 49.4 J / g. The corresponding CRYSTAF curve shows the tallest peak at 33.8 ° C. and a peak area of 7.7%. DSC delta T between T _m and _{Chris tarp} was 84.4 ℃.

The DSC curve for the polymer of Example 14 showed a peak with a melting point (T _m ) of 120.8 ° C. with a heat of fusion of 127.9 J / g. The corresponding CRYSTAF curve shows the tallest peak at 72.9 ° C. and a peak area of 92.2%. The delta between the DSC T _m and the T _crisp was 47.9 ° C.

The DSC curve for the polymer of Example 15 showed a peak with a melting point (T _m ) of 114.3 ° C. with a heat of fusion of 36.2 J / g. The corresponding CRYSTAF curve shows the tallest peak at 32.3 ° C. and a peak area of 9.8%. DSC delta T between T _m and _{Chris tarp} was 82.0 ℃.

The DSC curve for the polymer of Example 16 showed a peak with a melting point (T _m ) of 116.6 ° C. with a heat of fusion of 44.9 J / g. The corresponding CRYSTAF curve shows the tallest peak at 48.0 ° C. and a peak area of 65.0%. The delta between the DSC T _m and the T _crisp was 68.6 ° C.

The DSC curve for the polymer of Example 17 showed a peak with a melting point (T _m ) of 116.0 ° C. with a heat of fusion of 47.0 J / g. The corresponding CRYSTAF curve shows the highest peak at 43.1 ° C. and a peak area of 56.8%. DSC delta T between T _m and _{Chris tarp} was 72.9 ℃.

The DSC curve for the polymer of Example 18 showed a peak with a melting point (T _m ) of 120.5 ° C. with a heat of fusion of 141.8 J / g. The corresponding CRYSTAF curve shows the tallest peak at 70.0 ° C. and a peak area of 94.0%. The delta between the DSC T _m and the T-crystal was 50.5 ° C.

The DSC curve for the polymer of Example 19 showed a peak with a melting point (T _m ) of 124.8 ° C. with a heat of fusion of 174.8 J / g. The corresponding CRYSTAF curve shows the tallest peak at 79.9 ° C. and a peak area of 87.9%. The delta between the DSC T _m and the T _crisp was 45.0 ° C.

The DSC curve for the polymer of Comparative Example D ^* showed a peak with a melting point (T _m ) of 37.3 ° C. with a heat of fusion of 31.6 J / g. The corresponding CRYSTAF curve did not show a peak above 30 ° C. Both of these values were consistent with low density resins. The delta between the DSC T _m and the T _crisp was 7.3 ° C.

The DSC curve for the polymer of Comparative Example E ^* showed a peak with a melting point (T _m ) of 124.0 ° C. with a heat of fusion of 179.3 J / g. The corresponding CRYSTAF curve shows the tallest peak at 79.3 ° C. and a peak area of 94.6%. Both of these values were consistent with high density resins. The delta between the DSC T _m and the T _crisp was 44.6 ° C.

The DSC curve for the polymer of Comparative Example F ^* showed a peak with a melting point (T _m ) of 124.8 ° C. with a heat of fusion of 90.4 J / g. The corresponding CRYSTAF curve shows the tallest peak at 77.6 ° C. and a peak area of 19.5%. The spacing between the two peaks was consistent with the presence of both high and low crystalline polymers. The delta between the DSC T _m and the T _crisp was 47.2 ° C.

Property test

Polymer samples were evaluated for physical properties such as high temperature resistance exhibited by TMA temperature test, pelletized block strength, high temperature recovery rate, hot compressive strain rate and storage modulus ratio (G '(25 ° C) / G' (100 ° C)). . Several commercial polymers were included in the test. Comparative Example G ^* was a substantially linear ethylene / 1-octene copolymer (Affinity® available from The Dow Chemical Company), and Comparative Example H ^* was a substantially linear ethylene / 1-octene elastomer air Coalesce (Affinity® EG8100 available from The Dow Chemical Company) and Comparative Example I ^* were substantially linear ethylene / 1-octene copolymers (Affinity® available from The Dow Chemical Company). PL1840), Comparative Example J ^* was hydrogenated styrene / butadiene / styrene triblock copolymer (KRATON® G1652 available from KRATON Polymers) and Comparative Example K ^* was thermoplastic Vulcanizate (TPV, polyolefin blend with crosslinked elastomer dispersed). The results are shown in Table 4.

TABLE 4

In Table 4, Comparative Example F ^* (which is a physical blend of two polymers resulting from co-polymerization with Catalysts A1 and B1) has a 1 mm penetration temperature of about 70 ° C., while Examples 5-9 are 100 ° C. Had a penetration temperature of at least 1 mm. In addition, Examples 10-19 all had a 1 mm penetration temperature above 85 ° C., mostly with 1 mm TMA temperatures above 90 ° C. or even above 100 ° C. This shows that the new polymers have better dimensional stability at high temperatures compared to the physical blends. Comparative Example J ^* (commercially available SEBS) had a good 1 mm TMA temperature of about 107 ° C., but had a very poor (high temperature 70 ° C.) compression set of about 100%, which was also a high temperature (80 ° C.) 300% deformation. Recovery failed during recovery (sample failure). Thus, the polymers exemplified had a unique combination of properties not obtainable even in some commercially available high performance thermoplastic elastomers.

Similarly, Table 4 shows a low (good) storage modulus ratio (G '(25 ° C.) / G' (100 ° C.)) of 6 or less for the inventive polymers, while the physical blend (Comparative Example F ^* ) Shows that the storage modulus ratio is 9 and that the random ethylene / octene copolymer (Comparative Example G ^* ) of similar density has a storage modulus ratio 89 as large as one site. The storage modulus ratio of the polymer is preferably as close to 1 as possible. Such polymers are relatively unaffected by temperature, and articles comprising such polymers can be usefully used over a wide temperature range. This low storage modulus ratio and temperature independence feature is particularly useful in elastomer applications such as pressure sensitive adhesive formulations.

The data in Table 4 also demonstrates that the polymers of the present invention have improved pellet block strength. In particular, Example 5 has a pellet blocking strength of 0 MPa, which means free flowing under test conditions as compared to Comparative Examples F ^* and G ^* , which show significant blocking. Blocking strength is important because bulk shipments of polymers with large blocking strengths may result in the products clumping together or sticking during storage or shipping, resulting in poor handling properties.

The high temperature (70 ° C.) compression set is generally good for the polymers of the present invention, which generally means less than about 80%, preferably less than about 70%, in particular less than about 60%. On the other hand, Comparative Examples F ^* , G ^* , H ^* and J ^* all had a 70% compression set (meaning the maximum possible value, no recoverability) of 100%. Good high temperature compression set (low values) is particularly necessary for articles such as gaskets, window frames, o-rings, and the like.

TABLE 5

Table 5 shows the results for the mechanical properties at ambient temperature of the novel polymers as well as the various comparative polymers. It can be seen that the polymers of the present invention have very good wear resistance which, when tested according to ISO 4649, generally shows a volume loss of less than about 90 mm ³ , preferably less than about 80 mm ³ , in particular less than about 50 mm ³ . In this test, high values indicate high volume loss and consequently low wear resistance.

As shown in Table 5, the tear strength measured by the tensile notch tear strength of the polymer of the present invention was generally 1000 mJ or more. The tear strength of the polymers of the invention can be as high as 3000 mJ, or even as high as 5000 mJ. Comparative polymers generally had a tear strength of 750 mJ or less.

Table 5 also shows that the polymers of the present invention had better shrinkage stress at 150% strain compared to some of the comparative samples (represented by higher shrinkage stress values). Comparative Examples F ^* , G ^*, and H ^* have a shrinkage stress value of 400 kPa or less at 150% strain, whereas the polymer of the present invention has a shrinkage stress value at 500% of 150% strain (Example 11) to about 1100 kPa. (Example 17). Polymers with shrinkage stress values higher than 150% will be very useful for elastic articles such as elastic fibers and fabrics, especially nonwovens. Other uses include diapers, hygiene and medical garments, waistband articles such as tabs and elastic bands.

Table 5 also shows that the polymers of the invention have improved (lower) stress relaxation rates (at 50% strain), for example, compared to Comparative Example G ^* . Low stress relief means that the polymer has a better effect in applications such as diapers and other garments aimed at maintaining elasticity at body temperature for extended periods of time.

Optical test

TABLE 6

The optical properties reported in Table 6 are based on compression molded films that are substantially unoriented. The optical properties of the polymer can vary over a wide range due to changes in crystallite size due to changes in the amount of chain transfer agent used in the polymerization.

Extraction of Multi-Block Copolymers

Extraction studies were performed on the polymers of Examples 5, 7 and Comparative Example E ^* . In this experiment, polymer samples were weighed into a glass frit extraction thimble and placed in a Kumagawa type extractor. The extractor with sample was purged with nitrogen and a 50 mL round bottom flask was charged with 350 mL of diethyl ether. The flask was then fixed in the extractor. The ether was heated with stirring. The time when the ether began to condense into the extraction vessel was recorded and the extraction proceeded for 24 hours under nitrogen. At this time, heating was stopped and the solution was cooled. Any ether remaining in the extractor was returned to the flask. The ether in the flask was evaporated in vacuo at ambient temperature and the resulting solids were purged and dried with nitrogen. Any residue was transferred to a weighed bottle using a subsequent hexane wash. The combined hexane washes were then evaporated with additional nitrogen purge and the residue was dried in vacuo at 40 ° C. overnight. Any ether remaining in the extractor was purged to dryness with nitrogen.

Then another clean round bottom flask filled with 35 mL of hexane was connected to the extractor. The hexanes were heated to reflux with stirring and held at reflux for 24 hours after the first observation of hexane condensation into the extraction vessel. The heating was then stopped and the flask was cooled. Any hexane remaining in the extractor was transferred back to the flask. Hexane was removed by evaporation under vacuum at ambient temperature and any residue remaining in the flask was transferred to a weighed bottle using a subsequent hexane wash. Hexane in the flask was evaporated by nitrogen purge and the residue was vacuum dried at 40 ° C. overnight.

The polymer sample remaining in the extraction barrel after extraction was transferred to a weighed bottle in the barrel and vacuum dried overnight at 40 ° C. The results are shown in Table 7.

<Table 7>

Additional Polymer Examples 19 A to F, Continuous Solution Polymerization, Catalyst A1 / B2 + DEZ

Continuous solution polymerization was performed in a computer controlled well-mixed reactor. Purified mixed alkane solvent (Isopar ™ E) available from ExxonMobil Chemical Company, ethylene, 1-octene and hydrogen (if used) were combined and fed into a 27 gallon reactor. The feed to the reactor was measured by a mass-flow regulator. The temperature of the feed stream was controlled using a glycol cooled heat exchanger and then introduced into the reactor. The catalyst component solution was metered in using a pump and a mass flow meter. The reactor was run liquid-full at approximately 550 psig pressure. Upon exiting the reactor, water and additives were injected into the polymer solution. The polymerization was terminated by hydrolysis of the catalyst with water. The postreactor solution was then heated in preparation for the two stage devolatilization. The solvent and unreacted monomers were removed during the devolatilization process. The polymer melt was pumped into a die for cutting pellets underwater.

Process details and results are shown in Table 8A. Selected polymer properties are provided in Tables 8B and 8C.

TABLE 8A

¹ standard cm ³ / min

² [N- (2,6-di (1-methylethyl) phenyl) amido) (2-isopropylphenyl) (α-naphthalene-2-diyl (6-pyridine-2-diyl) methane)] hafnium dimethyl

³ bis- (1- (2-methylcyclohexyl) ethyl) (2-oxoyl-3,5-di (t-butyl) phenyl) imino) zirconium dimethyl

⁴ ppm in final product calculated by mass balance

⁵ Polymer Producing Rate

⁶ conversion of ethylene in the reactor (% by weight)

⁷ Efficiency, kg polymer / g M (where g M = g Hf + g Z)

TABLE 8B

TABLE 8C

Preparation Procedure of Polymer Example 20

The preparation procedure of Polymer Example 20 used in the Examples below was as follows. One gallon autoclave continuous stirred tank reactor (CSTR) was used for the experiment. The reactor was run full of liquid at about 540 psig with process flows inside the bottom and outside the top. The reactor was oil jacketed to assist in removing some of the heat of reaction. Primary temperature control was achieved by two heat exchangers on a solvent / ethylene addition line. Isopar® E, hydrogen, ethylene and 1-octene were fed to the reactor at a controlled feed rate.

The catalyst component was diluted in an air-free glove box. The two catalysts were fed separately from the different holding tanks in the desired proportions. To avoid plugging the catalyst feed line, the catalyst line and the cocatalyst line were separated and fed separately into the reactor. The cocatalyst was mixed with diethylzinc chain transfer agent before introduction into the reactor.

The main product was collected under stable reactor conditions. After a few hours, the product sample showed no substantial change in melt index or density. The product was stabilized with a mixture of Irganox® 1010, Irganox® 1076, and IrgaFOS® 176.

The structures of the two catalysts (ie catalysts Al and A2) used in the procedure are shown below:

Blend Embodiment Set 1

Blend compositions comprising Polymer Example 20, random ethylene / 1-octene copolymers and polypropylene (PPl) were prepared, evaluated and tested for properties. The following polymers were compared in the blend composition.

Polymer Example 20 has a composite 1-octene content of 77 wt%, a composite density of 0.854 g / cc, a DSC peak melting point of 105 ° C., a hard segment level of 6.8 wt% based on DSC measurement, ATREF The crystallization temperature is 73 ° C, the number average molecular weight is 188,254 daltons, the weight average molecular weight is 329,600 daltons, the melt index is 1.0 dg / min at 190 ° C, 2.16 Kg, and the melt index is 190 ° C, 37.0 dg at 10 kg It was an ethylene / 1-octene block copolymer which is / min. The polymer of Example 20 was prepared as described above.

Comparative Example A ¹ has a density of 0.87 g / cc, a 1-octene content of 38 wt%, a peak melting point of 59.7 ° C., a number average molecular weight of 59,000 daltons, a weight average molecular weight of 121,300 daltons, 190 ° C., It was a random ethylene / 1-octene copolymer whose melt index at 2.16 Kg was 1.0 dg / min and the melt index at 190 ° C. and 10 Kg was 7.5 dg / min. The product is marketed under the trade name ENGAGE 8100 from The Dow Chemical Company.

The polymers were melt mixed with PPl, a polypropylene homopolymer having a melt flow index of 2.0 dg / min at 230 ° C., 2.16 Kg, DSC melting point of 161 ° C., and a density of 0.9 g / cc. The product is sold under the trade name Dow Polypropylene Hl 10-02Ndm from The Dow Chemical Company. For all blends 0.2 parts per 100 parts total polymer, a 1: 1 blend of phenolic antioxidant / phosphite antioxidant (available under the tradename Irganox® B215) was added for thermal stability. The additive is indicated as AO in Table 9.

The following mixing procedure was used. A 69 cc capacity Haake batch mixing bowl equipped with a roller blade was heated to 200 ° C. for all zones. The mixing ball rotor speed was set to 30 rpm, filled with PPl, fluxed for 1 minute, then charged with AO and fluxed for an additional 2 minutes. The mixed balls were then filled with a 1: 1 blend of Polymer Example 20, Comparative Example A ¹ , or Polymer Example 20 and Comparative Example A ¹ . After adding the elastomer, the mixing ball rotor speed was increased to 60 rpm and mixed for an additional 3 minutes. The mixture is then removed from the mixing bowl, compressed between Mylar sheets, sandwiched between metal platens, and compressed in a Carver compression molding machine set to cool to a pressure of 20 kpsi at 15 ° C. I was. The cooled mixture was then compression molded into 2 inch X 2 inch X 0.06 inch plaques via compression molding for 3 minutes at 190 ° C, 2 kpsi pressure, 3 minutes at 190 ° C, 20 kpsi pressure, and then at 15 ° C, 20 Cooled at kpsi for 3 minutes. The mixtures prepared under the procedure described above are listed in Table 9.

TABLE 9

The compression molded plaques were trimmed so that the parts could be collected at the core. Prior to coloring the trimmed plaques the parts were cryopolished by removing them from the block at -60 ° C to prevent smearing of the elastomeric phase. The cryopolished blocks were colored with the vapor phase of a 2% aqueous ruthenium tetraoxide solution at ambient temperature for 3 hours. A coloring solution was prepared by weighing 0.2 g ruthenium (III) chloride hydrate (RuCl ₃ x H ₂ O) into a glass bottle with a screw lid and adding 5.25% aqueous sodium hypochlorite solution (10 ml) to the bottle. . Samples were placed into glass bottles using glass slides with double sided tape. The slides were placed in bottles so that the blocks hung about 1 inch above the coloring solution. Portions approximately 100 nanometers thick were collected at ambient temperature using a diamond knife on a Leica EM UC6 microtome and placed on a 400 mesh virgin TEM grating for observation.

Bright-Filed images were collected on a JEOL JEM 1230 transmission electron microscope operating at an accelerating voltage of 100 kV and collected using a Gatan 791 and a Gatan 794 digital camera. The image was post-processed using Adobe Photoshop 7.0.

10 and 11 are transmission electron micrographs of mixture 1 and mixture 2, respectively. Dark domains are RuCl ₃ XH ₂ O colored ethylene / 1-octene polymers. It can be seen that the domains containing Polymer Example 20 are much smaller than Comparative Example A ¹ . The domain size of Polymer Example 20 ranged from about 0.1 to about 2 μm, while the domain size of Comparative Example A ¹ was greater than about 0.2 to 5 μm. Mixture 3 contained a 1: 1 blend of Polymer Example 20 and Comparative Example A ¹ . It should be noted that polymer Example 20 improves the compatibility of PPl with Comparative Example A ¹ from that the domain size of mixture 3 is much smaller than that of mixture 2 by visual inspection.

Image analysis of mixtures 1, 2 and 3 was performed on 5kX TEM images using Leica Qwin Pro V2.4 software. The magnification selected for image analysis depends on the particle size and number to be analyzed. In consideration of binary image generation, manual tracking of elastomeric particles was performed from TEM prints using a black sharpie marker. The tracked TEM image was scanned using Hewlett Packard Scan Jet 4c to generate a digital image. Digital images were imported into the Leica Qwin Pro V2.4 program and converted to binary images by setting gray-level thresholds to include the features of interest. Once the binary image was generated, the image was edited using another processing tool before analyzing the image. Some of these features included manual cutting of features requiring soft feature removal, feature acceptance and exclusion, and separation. Once the particles in the image were measured, the sizing data was exported to an Excel spreadsheet that was used to generate a bin range of rubber particles. Sizing data was placed in the appropriate bin range and a histogram of particle length (maximum particle length) versus frequency (%) was generated. The parameters recorded were minimum, maximum, average particle size and standard deviation. Table 10 shows the image analysis results.

TABLE 10

From the above results, it can be seen that mixtures 1 and 2 both exhibit small average elastomer domain size and narrow domain size distribution. Advantageous interfacial effects could be seen from Polymer Example 20 as in 1: 1 blends with Comparative Example A ¹ in Mixture 3. The resulting domain average particle size and range are almost identical to Mixture 1 containing only Polymer Example 20 as the elastomer.

Blend Example Set 2

Polymer Example 21

The preparation procedure of Polymer Example 22 used in the Examples below is similar to the procedure used in Polymer Example 20, and the procedure was as follows. One gallon autoclave continuous stirred tank reactor (CSTR) was used for the experiment. The reactor was run full of liquid at about 540 psig with process flows inside the bottom and outside the top. The reactor was oil jacketed to assist in removing some of the heat of reaction. Primary temperature control was achieved by two heat exchangers on a solvent / ethylene addition line. Isopar® E, hydrogen, ethylene and 1-octene were fed to the reactor at a controlled feed rate.

The catalyst component was diluted in an air-free glove box. The two catalysts were fed separately from the different holding tanks in the desired proportions. To avoid plugging the catalyst feed line, the catalyst line and the cocatalyst line were separated and fed separately into the reactor. The cocatalyst was mixed with diethylzinc chain transfer agent before introduction into the reactor.

The main product was collected under stable reactor conditions. After a few hours, the product sample showed no substantial change in melt index or density. The product was stabilized with a mixture of Irganox® 1010, Irganox® 1076 and Irgaphos® 176.

TABLE 10

The structures of the two catalysts (ie catalysts Al and A2) used in the procedure are shown below:

Polymer Example 21 has a compound 1-octene content of 11.1 mol% (33 wt%), a compound density of 0.880 g / cc, a DSC peak melting point of 123 ° C., and a hard segment level of 0.4 mol% based on DSC measurements. (1.6 wt.%), ATREF crystallization temperature is 91 ° C., number average molecular weight is 43,600 g / mol, weight average molecular weight is 119,900 g / mol, melt index at 190 ° C., 2.16 Kg is about 1 dg / min Ethylene / 1-octene block copolymer.

Comparative Example B ^One

Comparative Example B ¹ has a density of 0.857 g / cc, a 1-octene content of 16.6 mol% (44 wt%), a peak melting point of 38 ° C., a number average molecular weight of 61,800 g / mol, and a weight average molecular weight of 124,300 and a random ethylene / 1-octene copolymer having a melt index of about 1 dg / min at 190 ° C and 2.16 Kg. The product is available from The Dow Chemical Company under the trade name Engage® 8842.

PP

PP is a polypropylene homopolymer having a melt flow index of 3.2 dg / min at 230 ° C., 2.16 Kg, a DSC melting point of 165 ° C. and a density of 0.9 g / cc.

HDPE

HDPE is a high density polyethylene homopolymer having a melt flow index of 0.80 dg / min at 230 ° C., 2.16 Kg, a DSC melting point of 133 ° C., and a density of 0.961 g / cc. The product is commercially available from The Dow Chemical Company under the trade name UNIVAL DMDH-6400 NT 7.

A melt blend having the compositions listed in Table 11 was prepared by adding a dry blend of the mixture to two preheated rotor ball mixers. A computer controlled Haake Polylab device was used to drive the ball with a Rheomix 600 model roller blade. The volume of the bowl was 69 ml. Dry blends were added via a separatory funnel with precalibration and preheated balls (230 ° C.) with a rotor running at 40 rpm. The ball was then sealed with an attached ram. After the mixture was melted in the bowl, the melted blend was mixed in the bowl for 10 minutes. At this time the rotor was stopped, the polymer blend was taken out and flattened in a lamination press. The cooled polymer patty was then cut into small squares for subsequent testing. Table 11 lists the mixtures and compositions.

TABLE 11

The blend was compression molded into a 15 mil thick film using a Carver hot press. These films were then sandwiched between Teflon sheets and heated at 190 ° C. for 9 minutes at 0.4 MPa. The blend was then cooled in water at ambient temperature.

Tapping mode atomic force microscopy (AFM) was used to study the phase morphology of the blend. The compression molded sample was first ground using an ultramicrotom (Reichert-Jung Ultracut E) at -100 ° C. perpendicular to the plaque near the center of the core region. Thin sections were placed on the mica surface for AFM imaging using DI NanoScope IV, MultiMode AFM, operating in tapping mode with phase detection. The tip was at a voltage of 3 V and the tapping ratio was 0.76 to 0.83. Nano-sensor tips with tip parameters were used: L = 235 μm, tip ratio = 5-10 nm, spring constant = 37-55 N / m, F ₀ = 159-164 kHz.

In the samples from Mixture 4 shown in FIG. 13, HDPE content in the PP matrix was observed. The domain size of HDPE ranged mainly from 1 to 10 μm with sharp interfaces. In Mixture 5 shown in FIG. 14 and Mixture 6 shown in FIG. 15, the addition of Comparative Example B ¹ or Polymer Example 21 reduced the HDPE domain size to less than 5 μm, respectively. The particles had a shell core morphology in which either Comparative Example B ¹ or Polymer Example 21 forms a shell and HDPE is the core. When the modulus of elasticity was low, Comparative Example B ¹ or Polymer Example 21 appeared as dark areas in the image. Individual particles of some Comparative Example B ¹ or Polymer Example 21 were also present.

Uniaxial tensile behavior was measured according to ASTM D 1708 using microtensile specimens at ambient temperature. Samples were stretched to Instron 5564 at a rate of 500% / min at a temperature of 21 ° C. Tensile strength and elongation at break were recorded from the average of five specimens.

Tensile curves of samples from mixtures 4, 5 and 6 are shown in FIG. 16. Samples from mixture 4 exhibited poor mechanical properties with low elongation at break (<200%) and low tensile strength (18 MPa). In the sample from Mixture 5 containing Comparative Example B ¹ , no improvement in final properties was observed despite the change in morphology. Yield stress was substantially reduced. In samples from Mixture 6 containing Polymer Example 21, a substantial improvement in tensile properties was observed compared to samples from Mixture 4 and Mixture 5. The sample from mixture 6 had a break elongation of about 860% with a tensile strength of about 41 MPa. The final properties are summarized in Table 12.

TABLE 12

Samples from mixtures 4, 5 and 6 were prepared via the following process for scanning electron microscopy (SEM). Small pieces from the compression molded plaques were cut into thin strips of approximately 50 mm x 8 mm. Razor notches were placed on both edges along the center of the strip to assist in the induction of straight bursts. The strip was fixed between the jaws of a pair of pliers and immersed in liquid nitrogen for approximately 5 minutes. Another set of pliers could be cooled simultaneously to rupture freeze quickly as the sample was taken out. Razor blades were used to remove excess polymer from under the tear so that the tear surface could be mounted on the sample mount. The fragment was placed on an aluminum SEM sample mount using double sided tape and carbon paint and sputtered with gold-palladium plasma for approximately 40 seconds.

Secondary electron images were collected on a Hitachi-4100 FEG scanning electron microscope using a 10 kV accelerating voltage. The image was post-processed using Adobe Photoshop 7.0.

17 and 18 are low magnification (approximately 3,000 ×) magnification and high magnification (approximately 30,000 ×) SEM images of the burst surface of the sample from mixture 4, respectively. Examination of the rupture surface revealed that interfacial debonding occurred with most HDPE domains. Examination at higher magnification (FIG. 18) showed that both voids and domain surfaces were present on the ruptured surface. Rupture did not seem to propagate through the mid-plane of the HDPE domain. The outer surface of the HDPE domain appeared to have a layered structure, and the inside of the hole looked relatively clean.

19 and 20 are low magnification (approximately 3,000 ×) and high magnification (approximately 30,000 ×) SEM images of the rupture surface of the sample of mixture 5, respectively. Examination of the rupture surface revealed that most of the HDPE domains were interfacial debonded. Examination at higher magnification (FIG. 20) showed that both voids and domain surfaces were present on the ruptured surface. The outer surface of the HDPE domain appeared to have a less textured structure and the inside of the hole looked relatively clean. Some interfacial bonds were observed, as can be seen by ligaments that exist along the domain-matrix interface. From the image, it can be seen that the interfacial adhesion between PP and HDPE is slightly improved. However, the total burst surface was still very similar to mixture 4.

21 and 22 are low magnification (approximately 3,000 ×) and high magnification (approximately 30,000 ×) SEM images of the burst surface of the sample of mixture 6, respectively. Examination of the rupture surface revealed that the domains dispersed on the rupture surface were not as clear as in the two blends. In addition, much less interfacial debonding was observed. Irradiation at higher magnifications (FIG. 22) revealed that the rupture mainly propagated through the commercialized HDPE domain. Although the sample broke freeze, local ductility was observed inside the HDPE domain. The bright features in the HDPE domain appeared to be the obtained and stretched polymer fibrils. From the image, it can be seen that there is a good interfacial adhesion between HDPE and PP.

Blend Example Set 3

Polymer Example 22

The preparation procedure of Polymer Example 22 used in the Examples below is similar to the procedure used in Polymer Example 20, and the procedure was as follows. One gallon autoclave continuous stirred tank reactor (CSTR) was used for the experiment. The reactor was run full of liquid at about 540 psig with process flows inside the bottom and outside the top. The reactor was oil jacketed to assist in removing some of the heat of reaction. Primary temperature control was achieved by two heat exchangers on a solvent / ethylene addition line. Isopar® E, hydrogen, ethylene and 1-octene were fed to the reactor at a controlled feed rate.

The catalyst component was diluted in an air-free glove box. The two catalysts were fed separately from the different holding tanks in the desired proportions. To avoid plugging the catalyst feed line, the catalyst line and the cocatalyst line were separated and fed separately into the reactor. The cocatalyst was mixed with diethylzinc chain transfer agent before introduction into the reactor.

The main product was collected under stable reactor conditions. After a few hours, the product sample showed no substantial change in melt index or density. The product was stabilized with a mixture of Irganox® 1010, Irganox® 1076 and Irgaphos® 176.

TABLE 13

The structures of the two catalysts (ie catalysts Al and A2) used in the procedure are shown below:

Polymer Example 22 has a composite 1-octene content of 9.1 mol% (29 wt%), a composite density of 0.892 g / cc, a DSC peak melting point of 120 ° C., and a 0.4 mole of hard segment level based on DSC measurements. % (1.6 wt.%), ATREF crystallization temperature is 100 ° C, number average molecular weight is 45,800 g / mol, weight average molecular weight is 90,800 g / mol, melt index at 190 ° C, 2.16 kg is 1.1 dg / min , 190 ° C., an ethylene / 1-octene block copolymer having a melt index of 1.1 dg / min.

A melt blend having the compositions listed in Table 14 was prepared by adding a dry blend of the mixture to two preheated rotor ball mixers. A computer controlled Hake Polylab apparatus was used to drive the ball with the Leomix 600 model roller blades. The volume of the bowl was 69 ml. Dry blends were added via a separatory funnel with precalibration and preheated balls (230 ° C.) with a rotor running at 40 rpm. The ball was then sealed with an attached ram. After the mixture was melted in the bowl, the melted blend was mixed in the bowl for 10 minutes. At this time the rotor was stopped, the polymer blend was taken out and flattened in a lamination press. The cooled polymer patty was then cut into small squares for subsequent testing. Table 14 lists the mixtures and compositions.

TABLE 14

The blend was compression molded into a 15 mil thick film using a Carver hot press. These films were then sandwiched between Teflon sheets and heated at 190 ° C. for 9 minutes at 0.4 MPa. The blend was then cooled in water at ambient temperature.

Tapping mode atomic force microscopy (AFM) was used to study the phase morphology of the blend. The compression molded sample was first ground using an ultramicrotome (Rachert-Jean Ultracut E) at −100 ° C. perpendicular to the plaque near the center of the core region. Thin sections were placed on the mica surface for AFM imaging using DI Nanoscope IV, multimode AFM, operating in tapping mode with phase detection. The voltage at the tip was 3 V, and the tapping ratio was 0.76 to 0.83. Nano-sensor tips with tip parameters were used: L = 235 μm, tip ratio = 5-10 nm, spring constant = 37-55 N / m, F ₀ = 159-164 kHz.

FIG. 23 is an AFM image of mixture 7, ie 70 parts of HDPE and 30 parts of Comparative Example B ¹ . The darker phase is a Comparative Example B ¹ -rich phase because it has a lower modulus than the HDPE phase. The phases exhibited some orientation that may be due to flow induced orientation during compression molding. 24 is an AFM image of Mixture 8. The darker phase is Comparative Example B ¹ -rich phase. It can be seen that polymer example 22 is compatible with low density polyethylene and high density polyethylene, as the phase size is smaller than mixture 7.

The tensile curves of the samples from mixture 7 and mixture 8 are shown in FIG. 25. Both blends showed similar stress strain curves. However, blends of commercialized mixture 8 had higher elongation at break and higher burst stress. Uniaxial tensile behavior was measured according to ASTM D 1708 using microtensile specimens at ambient temperature. Samples were stretched to Instron 5564 at a rate of 500% / min and a temperature of 21 ° C. Tensile strength and elongation at break are reported in Table 15 from the average of five specimens.

TABLE 15

FIG. 26 shows an AFM image of a sample of Mixture 9. FIG. The brighter phase is an HDPE-rich phase because it has a higher modulus of elasticity than the Comparative Example B ¹ -rich phase. The HDPE-rich phase is uniformly dispersed on the Comparative Example B ¹ -rich phase. At higher magnifications (FIG. 27), it was found that some of the layers were uniformly dispersed on Comparative Example B ¹ -rich. Without wishing to be bound by any particular theory, these layers may be any amount of low molecular weight HDPE and are believed to be miscible with Comparative Example B ¹ at high temperatures. However, upon cooling from high temperatures, they are further separated from the comparative example B ¹ -rich phase since the miscibility decreases with decreasing temperature. 28 and 29 are AFM images of Mixture 10. The morphology is similar to mixture 9 but with smaller HDPE-rich phases.

Tensile curves of samples of mixture 9 and mixture 10 are shown in FIG. 30. These exhibited almost the same stress strain behavior. Both blends exhibited elastomeric behavior and had high elongation at break.

TABLE 16

Additional Example

TABLE 17

In Table 17 above, HDPEl is a high density polyethylene having a density of 0.948 g / cc and a fractional melt index; HDPE2 is a high density polyethylene with a density of 0.953 and a melt index of 0.4; PPl is a polypropylene homopolymer with an MFR of 2.0; PP2 is polypropylene with an MFR of 0.5; OBCA is an olefin block copolymer having a density of 0.877 g / cc and a melt index of 0.5, and EO is an ethylene-octene random copolymer having a density of 0.902 g / cc and a melt index of 1.0. UHMWPE (37.5 kg, manufactured by GUIT 4120, manufactured by Ticona), mixtures 11-15 (25 kg each), lithium stearate (0.72 kg, manufactured by Norac) ), Antioxidant (0.59 kg, Irganox® B215, manufactured by Ciba), and plasticizer (111.1 kg, Hydrocal® 800, manufactured by Calumet) ) Were blended together in a Ross VMC-100 mixer in sequential batches using mixtures 11-15, respectively. Maleic anhydride-modified polyolefin powder (0.027 kg, manufactured by NE 556 P35, manufactured by Equistar) and additional plasticizer (0.91 kg) was added to 4.5 kg of the mixture to form a 30% w / w polymer slurry. It was. The slurry was pumped with a 40 mm twin screw extruder (manufactured by Betol) at a rate of approximately 5.4 kg / hr while maintaining a melting temperature of approximately 208 ° C. The extrudate was passed through a melt pump (37 rpm; 3 cc / rev) feeding a 49.5 mm diameter annular die with a 1.9 mm gap. The extrudate was expanded with air to produce a biaxially oriented film with a 356 mm layflat and a 300 mm neck length at 305 cm / min through the upper nip. 100 mm * 200 mm samples were cut from the plasticizer-filled sheet and fixed on four sides of the metal frame. The immobilized sample was extracted completely in a trichloroethylene (TCE) bath and dried at 80 ° C. in a circulating air oven to obtain a microporous film.

As demonstrated above, embodiments of the present invention provide various polymer blends with improved compatibility. Improved compatibility is achieved by adding the block interpolymers of the present invention to a mixture of two or more polyolefins that are relatively immiscible. Improved compatibility is evidenced by a reduction in average domain size, more uniform mixing and improved interfacial adhesion. Such blends should have a synergistic effect on the blend properties. These blends can be used to make the microporous film of the present invention.

Although the present invention has been described with respect to a limited number of embodiments, the specific features of one embodiment will not be attributed to other embodiments of the invention. A single embodiment does not represent all aspects of the invention. In some embodiments, a composition or method may comprise a number of compounds or steps not mentioned herein. In other embodiments, the compositions or methods do not comprise or substantially have any compounds or steps not listed herein. There are variations and modifications from the described embodiments. Finally, any number described herein should be interpreted to mean approximate, regardless of whether the word "about" or "approximately" is used to describe that number. It is intended that the appended claims cover all such modifications and variations as fall within the scope of the present invention.

Claims (11)

(i) a first polymer; (ii) a second polymer; And (iii) a polymeric compatibilizer comprising an effective amount of an ethylene / a-olefin interpolymer having one or more of the following features A microporous film comprising at least one layer comprising a polymer blend comprising: (a) Mw / Mn of about 1.7 to about 3.5, at least one melting point T _m (° C.), and density d (g / cm ³ ), where the values of T _m and d correspond to the following relationship: T _m > -2002.9 + 4538.5 (d) -2422.2 (d) ² ); or (b) Delta value ΔT (° C.), defined as the Mw / Mn of about 1.7 to about 3.5, and the heat of fusion ΔH (J / g), and the temperature difference between the highest DSC peak and the highest CRYSTAF peak (Where the values of ΔT and ΔH have the following relationship: ΔT> -0.1299 (ΔH) + 62.81 (if ΔH is greater than 0 and less than or equal to 130 J / g), ΔT ≧ 48 ° C. (if ΔH is greater than 130 J / g); The crisp peak is determined using at least 5% of the cumulative polymer, and if less than 5% of the polymer has an identified crisp peak, the crisp temperature is 30 ° C.); or (c) 300% strain and elastic recovery rate Re (%) at 1 cycle, and density d (g / cm ³ ) measured with a compression-molded film of ethylene / α-olefin interpolymers, wherein the values of Re and d Satisfies the following relationship when the ethylene / α-olefin interpolymer is substantially free of the crosslinked phase: Re> 1481-1629 (d)); or (d) molecular fractions eluted at 40 ° C. to 130 ° C. when fractionated using TREF (the fractions having at least 5% higher comonomer molar content than that of the comparative random ethylene interpolymer fractions eluting between the same temperatures) Wherein the comparative random ethylene interpolymer has the same comonomer (s) and has a melt index, density and comonomer molar content (based on total polymer) within 10% of that of the ethylene / α-olefin interpolymers ); or (e) storage modulus G '(25 ° C.) at 25 ° C., and storage modulus G' (100 ° C.) at 100 ° C., where the ratio of G ′ (25 ° C.) to G ′ (100 ° C.) is about 1: In the range from 1 to about 9: 1); or (f) at least one molecular fraction characterized by having a block index of at least 0.5 to about 1 and a molecular weight distribution Mw / Mn of greater than about 1.3 and eluting at 40 ° C. to 130 ° C. when fractionated using TREF; or (g) an average block index greater than 0 and up to about 1.0 and a molecular weight distribution Mw / Mn greater than about 1.3; or (h) Mw / Mn from about 1.7 to about 3.5, at least one melting point T _m (° C.), and density d (g / cm ³ ), where the values of T _m and d correspond to the following relationship: T _m > -6553.3 + 13735 (d) -7051.7 (d) ² ). The microporous film of claim 1 or 2, wherein (i) and / or (ii) comprises a polyolefin. (I) and / or (ii) are low density polypropylene (LDPP), high density polypropylene (HDPP), high melt strength polypropylene (HMS-PP), high impact polypropylene (HIPP), iso A microporous film selected from the group consisting of tactic polypropylene (iPP), syndiotactic polypropylene (sPP), and combinations thereof. The microporous film of claim 2, wherein (i) and / or (ii) comprises high density polyethylene (HDPE) and the second polymer comprises low density polyethylene (LDPE) or linear low density polyethylene (LLDPE). The microporous film of claim 2, wherein (i) and / or (ii) comprises high density polyethylene (HDPE) and the second polymer comprises an ethylene copolymer having a composition distribution width index CDBI of greater than 50%. The microporous film of claim 1, wherein (i) and / or (ii) comprises vulcanizable rubber. 7. The apparatus of claim 1, further comprising a first non-coextruded portion and a second non-coextruded portion, wherein the first portion is directly bonded to the second portion. The bond has a strength of greater than 5 g / inch and the first portion and the second portion are made of the same material and are oriented substantially in the same direction); Microporous film having a thickness of less than 1.5 mils, a Gurley value of less than 50 seconds / 10 cc and a puncture strength of greater than 400 g / mil. The microporous film of claim 1, wherein the polymer is functionalized. The microporous film of claim 1, further comprising an additional layer. The separator containing the microporous film of any one of Claims 1-9. An article comprising the microporous film of claim 1.

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